EP3333172A1 - Silane compound containing perfluoro(poly)ether group - Google Patents
Silane compound containing perfluoro(poly)ether group Download PDFInfo
- Publication number
- EP3333172A1 EP3333172A1 EP16832716.1A EP16832716A EP3333172A1 EP 3333172 A1 EP3333172 A1 EP 3333172A1 EP 16832716 A EP16832716 A EP 16832716A EP 3333172 A1 EP3333172 A1 EP 3333172A1
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- European Patent Office
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- Prior art date
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- -1 Silane compound Chemical class 0.000 title claims abstract description 75
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 55
- 125000001033 ether group Chemical group 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims description 74
- 239000003795 chemical substances by application Substances 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 61
- 125000004432 carbon atom Chemical group C* 0.000 claims description 45
- 125000000217 alkyl group Chemical group 0.000 claims description 39
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 27
- 229910052731 fluorine Inorganic materials 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 125000000962 organic group Chemical group 0.000 claims description 25
- 125000001153 fluoro group Chemical group F* 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 230000003287 optical effect Effects 0.000 claims description 16
- 229920002545 silicone oil Polymers 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 13
- 238000001771 vacuum deposition Methods 0.000 claims description 13
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims description 6
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 4
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 4
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 55
- 238000000576 coating method Methods 0.000 description 37
- 239000010702 perfluoropolyether Substances 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 238000000034 method Methods 0.000 description 17
- 239000002243 precursor Substances 0.000 description 17
- 239000003921 oil Substances 0.000 description 15
- 239000010408 film Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000002194 synthesizing effect Effects 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 8
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 230000003373 anti-fouling effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000003426 chemical strengthening reaction Methods 0.000 description 4
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000005052 trichlorosilane Substances 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 3
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- KSOCRXJMFBYSFA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,6,6,6-tridecafluoro-5-(1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluorohexan-2-yloxy)hexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KSOCRXJMFBYSFA-UHFFFAOYSA-N 0.000 description 2
- PGISRKZDCUNMRX-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-(trifluoromethoxy)butane Chemical compound FC(F)(F)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F PGISRKZDCUNMRX-UHFFFAOYSA-N 0.000 description 2
- NOPJRYAFUXTDLX-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane Chemical compound COC(F)(F)C(F)(F)C(F)(F)F NOPJRYAFUXTDLX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 2
- 229910003872 O—Si Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 125000001339 silanediyl group Chemical group [H][Si]([H])(*)* 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- BRWBDEIUJSDQGV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-methoxyhexane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BRWBDEIUJSDQGV-UHFFFAOYSA-N 0.000 description 1
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- QIROQPWSJUXOJC-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6-undecafluoro-6-(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F QIROQPWSJUXOJC-UHFFFAOYSA-N 0.000 description 1
- IDBYQQQHBYGLEQ-UHFFFAOYSA-N 1,1,2,2,3,3,4-heptafluorocyclopentane Chemical compound FC1CC(F)(F)C(F)(F)C1(F)F IDBYQQQHBYGLEQ-UHFFFAOYSA-N 0.000 description 1
- XXZOEDQFGXTEAD-UHFFFAOYSA-N 1,2-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1C(F)(F)F XXZOEDQFGXTEAD-UHFFFAOYSA-N 0.000 description 1
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 125000001313 C5-C10 heteroaryl group Chemical group 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910004721 HSiCl3 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910009973 Ti2O3 Inorganic materials 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000005400 gorilla glass Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000006341 heptafluoro n-propyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- LOQGSOTUHASIHI-UHFFFAOYSA-N perfluoro-1,3-dimethylcyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)C1(F)F LOQGSOTUHASIHI-UHFFFAOYSA-N 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/165—Macromolecular compounds containing hydrolysable groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
- B05D2203/35—Glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2350/00—Pretreatment of the substrate
- B05D2350/60—Adding a layer before coating
- B05D2350/63—Adding a layer before coating ceramic layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/76—Hydrophobic and oleophobic coatings
Definitions
- the present invention relates to a perfluoro(poly)ether group containing silane compound.
- a certain fluorine-containing silane compound is known to be able to provide excellent water-repellency, oil-repellency, antifouling property, or the like when it is used in a surface treatment of a base material.
- a layer (hereinafter, referred to as a "surface-treating layer") formed from a surface-treating agent comprising a fluorine-containing silane compound is applied to various base materials such as a glass, a plastic, a fiber and a building material as a so-called functional thin film.
- Patent Documents 1 and 2 a perfluoropolyether group containing silane compound which has a perfluoropolyether group in its main molecular chain and a hydrolyzable group bonding to a Si atom in its molecular terminal or terminal portion is known (Patent Documents 1 and 2).
- the surface-treating layer is requested for high durability to provide a base material with a desired function for a long time.
- the layer formed from the surface-treating agent containing the perfluoropolyether group containing silane compound has been suitably used in an optical member such as glasses, a touch panel or the like which is required to have light permeability or transparency since it can exert the above functions even in form of a thin film.
- the friction durability is required to be further improved.
- a layer formed from a surface-treating agent containing a conventional perfluoropolyether group containing silane compound described above is no longer necessarily enough to meet the increasing demand to improve the friction durability.
- An object of the present invention is to provide a perfluoro(poly)ether group containing silane compound which is able to form a layer having water-repellency, oil-repellency and antifouling property as well as high friction durability.
- a surface-treating agent comprising the perfluoro(poly)ether group containing silane compound described above.
- a pellet comprising the surface-treating agent described above.
- an article comprising a base material and a layer which is formed on a surface of the base material from the perfluoro(poly)ether group containing silane compound described above or the surface-treating agent described above.
- a novel perfluoro(poly)ether group containing silane compound Furthermore, there is provided a surface treating agent obtained by using the perfluoro(poly)ether group containing silane compound. By using them, the surface-treating layer having water-repellency, oil-repellency and antifouling property as well as excellent friction durability can be formed.
- a “hydrocarbon group” as used herein represents a group containing a carbon atom and a hydrogen atom which is obtained by removing a hydrogen atom from a hydrocarbon.
- the hydrocarbon group include, but are not particularly limited to, a hydrocarbon group having 1-20 carbon atoms which may be substituted with one or more substituents, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and the like.
- the "aliphatic hydrocarbon group” may be straight, branched or cyclic, and may be saturated or unsaturated.
- the hydrocarbon group may contain one or more ring structures. It is noted that the hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, or the like at its end or in its molecular chain.
- examples of the substituent of the "hydrocarbon group” include, but are not particularly limited to, for example a halogen atom; and a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, a C 3-10 unsaturated cycloalkyl group, a 5-10 membered heterocyclyl group, a 5-10 membered unsaturated heterocyclyl group, a C 6-10 aryl group, a 5-10 membered heteroaryl group, and the like, which may be substituted by one or more halogen atoms.
- an "organic group” represents a group containing a carbon atom.
- a “2-10 valent organic group” represents a 2-10 valent group containing a carbon atom.
- Examples of the 2-10 valent organic group include, but are not particularly limited to, a 2-10 valent group obtained by removing 1-9 hydrogen atoms from a hydrocarbon group.
- examples of the divalent organic group include, but are not particularly limited to, a divalent group obtained by removing one hydrogen atom from a hydrocarbon group from a hydrocarbon group.
- the present invention provides a perfluoro(poly)ether group (hereinafter, also referred to as "PFPE”) containing silane compound of the formula (1a) or the formula (1b) (hereinafter, also referred to as "a PFPE containing silane compound of the present invention”).
- PFPE perfluoro(poly)ether group
- Rf-PFPE ⁇ -X-(CR a k R b l R c m ) ⁇ ⁇ (1a)
- R c m R b l R a k C ⁇ -X-PFPE-X-(CR a k R b l R c m ) ⁇ ⁇ (1b)
- Rf is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms.
- alkyl group having 1-16 carbon atoms in the alkyl having 1-16 carbon atoms which may be substituted by one or more fluorine atoms may be straight or branched, and preferably is a straight or branched alkyl group having 1-6 carbon atoms, in particular 1-3 carbon atoms, more preferably a straight alkyl group having 1-3 carbon atoms.
- Rf is preferably an alkyl having 1-16 carbon atoms substituted by one or more fluorine atoms, more preferably a CF 2 H-C 1-15 fluoroalkylene group, more preferably a perfluoroalkyl group having 1-16 carbon atoms.
- the perfluoroalkyl group having 1-16 carbon atoms may be straight or branched, and preferably is a straight or branched perfluoroalkyl group having 1-6 carbon atoms, in particular 1-3 carbon atoms, more preferably a straight perfluoroalkyl group having 1-3 carbon atoms, specifically -CF 3 , -CF 2 CF 3 or -CF 2 CF 2 CF 3 .
- PFPE is -(OC 4 F 8 ) a -(OC 3 F 6 ) b -(OC 2 F 4 ) c -(OCF 2 ) d -, and corresponds to a perfluoro(poly)ether group.
- a, b, c and d are each independently 0 or an integer of 1 or more.
- the sum of a, b, c and d is 1 or more.
- a, b, c and d are each independently an integer of 0 or more and 200 or less, for example an integer of 1 or more and 200 or less, more preferably each independently an integer of 0 or more and 100 or less, for example an integer of 1-200.
- a, b, c and d is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
- the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula.
- the -(OC 4 F 8 )-group may be any of -(OCF 2 CF 2 CF 2 CF 2 )-, - (OCF(CF 3 )CF 2 CF 2 )-,-(OCF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF(CF 3 ))-, - (OC(CF 3 ) 2 CF 2 )-,-(OCF 2 C(CF 3 ) 2 )-, -(OCF(CF 3 )CF(CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and-(OCF 2 CF(C 2 F 5 ))-, preferably -(OCF 2 CF 2 CF 2 CF 2 )-.
- the - (OC 3 F 6 )-group may be any of - (OCF 2 CF 2 CF 2 )-, - (OCF(CF 3 )CF 2 )- and-(OCF 2 CF(CF 3 ))-, preferably -(OCF 2 CF 2 CF 2 )-.
- the -(OC 2 F 4 )-group may be any of -(OCF 2 CF 2 )- and -(OCF(CF 3 ))-, preferably -(OCF 2 CF 2 )-.
- PFPE is -(OC 3 F 6 ) b - wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, preferably -(OCF 2 CF 2 CF 2 ) b - wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, or - (OCF(CF 3 )CF 2 ) b - wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, more preferably - (OCF 2 CF 2 CF 2 ) b - wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, more preferably 10 or more and 200 or less.
- PFPE is -(OC 4 F 8 ) a -(OC 3 F 6 ) b -(OC 2 F 4 ) c -(OCF 2 ) d - wherein a and b are each independently an integer of 0 or more and 30 or less, c and d are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula; preferably -(OCF 2 CF 2 CF 2 CF 2 ) a -(OCF 2 CF 2 CF 2 ) b -(OCF 2 CF 2 ) c -(OCF 2 ) d -.
- PFPE may be -(OC 2 F 4 ) c -(OCF 2 ) d - wherein c and d are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and the occurrence order of the respective repeating units in parentheses with the subscript c or d is not limited in the formula.
- a lower limit of a ratio of c to d (hereinafter, referred to as an "c/d ratio”) may be 0.2, preferably 0.3, and an upper limit of the c/d ratio may be 1.5, preferably 1.3, more preferably 1.1, further preferably 0.9.
- c/d ratio a ratio of c to d
- an upper limit of the c/d ratio may be 1.5, preferably 1.3, more preferably 1.1, further preferably 0.9.
- PFPE is a group of - (OC 2 F 4 -R 8 ) n" -.
- R 8 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or a combination of 2 or 3 groups independently selected from these groups.
- Examples of the combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 include, but not limited to, for example, -OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 4 F 8 -, -OC 3 F 6 OC 2 F 4 -,-OC 3 F 6 OC 3 F 6 -, -OC 3 F 6 OC 4 F 8 -, -OC 4 F 8 OC 4 F 8 -, -OC 4 F 8 OC 3 F 6 -,-OC 4 F 8 OC 2 F 4 -, -OC 2 F 4 OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 2 F 4 OC 4 F 8 -,-OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 2 F 4 OC 4 F 8 -,-OC 2 F 4 OC 3 F 6 -, -
- n" is an integer of 2-100, preferably an integer of 2-50.
- OC 2 F 4 , OC 3 F 6 and OC 4 F 8 may be straight or branched, preferably straight.
- PFPE is preferably -(OC 2 F 4 -OC 3 F 6 ) n" - or -(OC 2 F 4 -OC 4 F 8 ) f -.
- X is each independently a single bond or a 2-10 valent organic group.
- X is recognized to be a linker which connects between a perfluoropolyether moiety (i.e., an Rf-PFPE moiety or -PFPE- moiety) providing mainly water-repellency, surface slip property and the like and a moiety (i.e., a group in parentheses with the subscript ⁇ ) providing an ability to bind to a base material in the compound of the formula (1a) and (1b). Therefore, X may be any organic group as long as the compound of the formula (1a) and (1b) can stably exist.
- a perfluoropolyether moiety i.e., an Rf-PFPE moiety or -PFPE- moiety
- a moiety i.e., a group in parentheses with the subscript ⁇
- ⁇ is an integer of 1-9, and ⁇ is an integer of 1-9.
- ⁇ and ⁇ may be varied depending on the valence number of the X group.
- the sum of ⁇ and ⁇ is the valence number of X.
- ⁇ is a value obtained by subtracting 1 from the valence number of X.
- X is preferably a 2-7 valent, more preferably 2-4 valent, more preferably a divalent organic group.
- X is a 2-4 valent organic group
- ⁇ is 1-3
- ⁇ is 1.
- X is a divalent organic group
- ⁇ is 1
- ⁇ is 1.
- the formulae (1a) and (1b) are represented by the following formulae (1a') and (1b').
- X examples include, but are not particularly limited to, for example a divalent group of the following formula: -(R 31 ) p' -(X a ) q' - wherein:
- X is a C 1-20 alkylene group, -R 31 -X c -R 31 -, or -X d -R 31 - wherein R 31 is as defined above.
- X is an C 1-20 alkylene group, - (CH 2 ) s' -X c -, -(CH 2 ) s' -X c -(CH 2 ) t' - -X d -, or -x d -(CH 2 ) t' - wherein s' and t' are as defined above.
- X c is -O-, -S-, -C(O)O-, -CONR 34 -, -O-CONR 34 -, -Si(R 33 ) 2 -, -(Si(R 33 ) 2 O) m' -Si(R 33 ) 2 -, -O-(CH 2 ) u' -(Si(R 33 ) 2 O) m' -Si(R 33 ) 2 -, -O-(CH 2 ) u' -Si(R 33 ) 2 -O-Si(R 33 ) 2 -CH 2 CH 2 -Si(R 33 ) 2 -O-Si(R 33 ) 2 -, -O-(CH 2 ) u' -Si(OCH 3 ) 2 OSi(OCH 3 ) 2 -, -CONR 34 -(CH 2 ) u' -(Si(R 33 ) 2
- X d is -S-, -C(O)O-, -CONR 34 -, -CONR 34 -(CH 2 ) u' -(Si(R 33 ) 2 O) m' -Si(R 33 ) 2 -, -CONR 34 -(CH 2 ) u' -N(R 34 )-, or -CONR 34 -(o-, m- or p-phenylene)-Si(R 33 ) 2 - wherein each of symbols is as defined above.
- X is an C 1-20 alkylene group, -(CH 2 ) s' -X c -(CH 2 ) t' -, or -X d -(CH 2 ) t' - wherein each of symbols is as defined above.
- X is an C 1-20 alkylene group, -(CH 2 ) s' -O-(CH 2 ) t' -, -(CH 2 ) s' -(Si(R 33 ) 2 O) m' -Si(R 33 ) 2 -(CH 2 ) t' -, -(CH 2 ) s' -O-(CH 2 ) u' -(Si(R 33 ) 2 O)-Si(R 33 ) 2 -(CH 2 ) t' -, or -(CH 2 ) s' -O-(CH 2 ) t' -Si(R 33 ) 2 -(CH 2 ) u' -Si(R 33 ) 2 -(C v H 2v )- wherein R 33 , m', s', t' and u' are as defined above, and v is an integer of 1-20, preferably an integer of 2
- -(C v H 2v )- may be straight or branched, for example, may be, for example, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -,-CH(CH 3 )-, -CH(CH 3 )CH 2 -.
- X may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group (preferably, a C 1-3 perfluoroalkyl group).
- examples of X include, for example, the following groups:
- X include, for example:
- X is each independently a 3-10 valent organic group.
- examples of X include the following groups:
- R a is each independently at each occurrence -Z-CR 1 p R 2 q R 3 r .
- Z is each independently at each occurrence, an oxygen atom or a divalent organic group.
- Z is preferably a C 1-6 alkylene group, - (CH 2 ) g -O-(CH 2 ) h -(wherein g is an integer of 0-6, for example, an integer of 1-6, h is an integer of 0-6, for example, an integer of 1-6) or -phenylene-(CH 2 ) i - (wherein i is an integer of 0-6), more preferably a C 1-3 alkylene group.
- These groups may be substituted with, for example, one or more substituents selected form a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group.
- R 1 is each independently at each occurrence R a' .
- R a' is as defined for R a .
- the number of C atoms which are linearly connected via Z is up to five. That is, in R a , when there is at least one R 1 , there are two or more C atoms which are linearly connected via Z in R a . The number of such C atoms which are linearly connected via Z is five at most. It is noted that "the number of such C atoms which are linearly connected via Z in R a is equal to the repeating number of - Z-C- which are linearly connected in R a .
- * represents a position binding to C of the main backbone
- ... represents that a predetermined group other than ZC binds thereto, that is, when all three bonds of a C atom are ..., it means an end point of the repeat of ZC.
- the number on the right shoulder of C means the number of occurrences of C which is linearly connected via the Z group from *. In other words, in the chain in which the repeat of ZC is completed at C 2 , "the number of such C atoms which are linearly connected via the Z group in R a " is 2.
- the number of such C atoms which are linearly connected via the Z group in R a is 1 (left formula) or 2 (right formula) in all chains.
- the number of such C atoms which are linearly connected via the Z group in R a is 1 or 2, preferably 1.
- R 2 is -Y-SiR 5 n R 6 3-n .
- Y is each independently at each occurrence a divalent organic group.
- Y is a C 1-6 alkylene group, -(CH 2 ) g' -O-(CH 2 ) h' - (wherein g' is an integer of 0-6, for example, an integer of 1-6, and h' is an integer of 0-6, for example, an integer of 1-6), or -phenylene-(CH 2 ) i' -(wherein i' is an integer of 0-6).
- These groups may be substituted with, for example, one or more substituents selected form a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group.
- Y may be a C 1-6 alkylene group, -O-(CH 2 ) h' - or -phenylene-(CH 2 ) i' -
- a light resistance in particular an ultraviolet resistance, may be increased.
- R 5 is each independently at each occurrence a hydroxyl group or a hydrolyzable group.
- hydrolyzable group represents a group which is able to undergo a hydrolysis reaction.
- R examples include a non-substituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group; a substituted alkyl group such as a chloromethyl group.
- an alkyl group in particular a non-substituted alkyl group is preferable, a methyl group or an ethyl group is more preferable.
- the hydroxyl group may be, but is not particularly limited to, a group generated by hydrolysis of a hydrolyzable group.
- R 5 is -OR wherein R is a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl group or a methyl group, in particular a methyl group.
- R 6 is each independently at each occurrence a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1-20 carbon atoms, more preferably an alkyl group having 1-6 carbon atoms, further preferably a methyl group.
- n is an integer of 1-3, preferably 2 or 3, more preferably 3, independently per unit -Y-SiR 5 n R 6 3-n .
- R 3 is each independently at each occurrence a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1-20 carbon atoms, more preferably an alkyl group having 1-6 carbon atoms, further preferably a methyl group.
- the sum of p, q and r is 3.
- q is preferably 2 or more, for example 2 or 3, more preferably 3.
- R b is each independently at each occurrence -Y-SiR 5 n R 6 3-n .
- Y, R 5 , R 6 and n are as defined for R 2 .
- R c is each independently at each occurrence a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1-20 carbon atoms, more preferably an alkyl group having 1-6 carbon atoms, further preferably a methyl group.
- the sum of k, 1 and m is 3.
- At least one k is 2 or 3, preferably 3.
- k is 2 or 3, preferably 3.
- 1 is 2 or 3, preferably 3.
- At least one q is 2 or 3, or at least one 1 is 2 or 3. That is, there are at least two -Y-SiR 5 n R 6 3-n groups in the formula.
- an average molecular weight of the Rf-PFPE moiety is not particularly limited to, and is 500 ⁇ 30,000, preferably 1,500-30,000, more preferably 2,000-10,000.
- the perfluoro(poly)ether group containing silane compound of the formula (1a) or the formula (1b) may have, but are not limited to, an average molecular weight of 5 x 10 2 - 1 x 10 5 .
- the compound has preferably 2,000-32,000, more preferably 2,500-12,000. It is noted that the "average molecular weight" in the present invention means a number average molecular weight, and the "average molecular weight” is defined as a value measured by using 19 F-NMR.
- the perfluoro(poly)ether group containing silane compound of the formula (1a) or the formula (1b) can be prepared by a combination of known methods.
- a compound of the formula (1a') wherein X is a divalent group can be prepared below, although the present invention is not limited thereto.
- the surface-treating agent of the present invention comprises at least one the perfluoro(poly)ether group containing silane compound of the formula (1a) or the formula (1b).
- the surface-treating agent of the present invention can provide a base material with water-repellency, oil-repellency, antifouling property, surface slip property and friction durability, and can be suitably used as an antifouling-coating agent or a water-proof coating agent, although the present invention is not particularly limited thereto.
- the surface-treating agent of the present invention comprises at least one compound of the formula (1a) or the formula (1b) wherein x is a divalent organic group, ⁇ and ⁇ are 1.
- the surface-treating agent of the present invention comprises at least one compound of the formula (1a) or the formula (1b) wherein 1 is 3 and n is 3.
- the surface-treating agent of the present invention comprises the compound of the formula (1a) .
- the above-mentioned surface-treating agent may comprise other components in addition to the compound of the formula (1a) or the formula (1b).
- the other components include, but are not particularly limited to, for example, a (non-reactive) fluoropolyether compound which may be also understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter, referred to as "the fluorine-containing oil”), a (non-reactive) silicone compound which may be also understood as a silicone oil (hereinafter referred to as "a silicone oil”), a catalyst, and the like.
- fluorine-containing oil examples include, but are not particularly limited to, for example, a compound of the following general formula (3) (a perfluoro(poly)ether compound).
- R 21 represents a C 1-16 alkyl group which may be substituted by one or more fluorine atoms (preferably, a C 1-16 perfluoroalkyl group)
- R 22 represents a C 1-16 alkyl group which may be substituted by one or more fluorine atoms (preferably, a C 1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, and more preferably, R 21 and R 22 is each independently a C 1-3 perfluoroalkyl group.
- Subscripts a', b', c' and d' represent the repeating number of each of four repeating units of perfluoropolyether which constitute a main backbone of the polymer, and are each independently an integer of 0 or more and 300 or less, and the sum of a', b', c' and d' is at least 1, preferably 1-300, more preferably 20-300.
- the occurrence order of the respective repeating units in parentheses with the subscript a', b', c' or d' is not limited in the formulae.
- the -(OC 4 F 8 )- group may be any of -(OCF 2 CF 2 CF 2 CF 2 )-,-(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF(CF 3 ))-,-(OC(CF 3 ) 2 CF 2 )-, -(OCF 2 C(CF 3 ) 2 )-, - (OCF(CF 3 )CF(CF 3 ))-,-(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-, preferably-(OCF 2 CF 2 CF 2 CF 2 ).
- the -(OC 3 F 6 )- group may be any of - (OCF 2 CF 2 CF 2 )-, - (OCF(CF 3 )CF 2 )- and -(OCF 2 CF(CF 3 ))-, preferably - (OCF 2 CF 2 CF 2 )-.
- the -(OC 2 F 4 )- group may be any of -(OCF 2 CF 2 )- and -(OCF(CF 3 ))-, preferably -(OCF 2 CF 2 )-.
- Examples of the perfluoropolyether compound of the above general formula (3) include a compound of any of the following general formulae (3a) and (3b) (may be one compound or a mixture of two or more compounds).
- R 21 -(OCF 2 CF 2 CF 2 ) b" -R 22 (3a) R 21 -(OCF 2 CF 2 CF 2 ) a" -(OCF 2 CF 2 CF 2 ) b" -(OCF 2 CF 2 ) c" -(OCF 2 ) d" -R 22 (3b)
- R 21 and R 22 are as defined above; in the formula (3a), b" is an integer of 1 or more and 100 or less; and in the formula (3b), a" and b" are each independently an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less.
- the above-mentioned fluorine-containing oil may have an average molecular weight of 1,000-30,000. By having such average molecular weight, high surface slip property can be obtained.
- the fluorine-containing oil may be contained in the surface-treating agent of the present invention, for example, at 0-500 parts by mass, preferably 0-400 parts by mass, more preferably 25-400 parts by mass with respect to 100 parts by mass of the PFPE containing silane compound of the present invention (as the total mass when two or more compounds are used; hereinafter the same shall apply).
- the compound of the general formula (3a) and the compound of the general formula (3b) may be used alone or in combination.
- the compound of the general formula (3b) is preferable than the compound of the general formula (3a) since the compound of the general formula (3b) provides higher surface slip property than the compound of the general formula (3a).
- the ratio by mass of the compound of the general formula (3a) to the compound of the general formula (3b) is preferably 1:1 to 1:30, more preferably 1:1 to 1:10. By applying such ratio by mass, a perfluoropolyether group-containing silane-based coating which provides a good balance of surface slip property and friction durability can be obtained.
- the fluorine-containing oil comprises one or more compounds of the general formula (3b).
- the mass ratio of the compound of the formula (1a) or the formula (1b) to the compound of the formula (3b) in the surface-treating agent is preferably 4:1 to 1:4.
- the surface-treating agent of the present invention comprises the compound of the formula (1a) or the formula (1b) wherein PFPE is - (OCF 2 CF 2 CF 2 ) b - (b is an integer of 1-200) and the compound of the formula (3b).
- the surface-treating agent of the present invention comprises the compound wherein PFPE represents -(OC 4 F 8 ) a -(OC 3 F 6 ) b -(OC 2 F 4 ) c -(OCF 2 ) d -wherein a and b are each independently an integer of 0 or more and 30 or less, preferably 0 or more and 10 or less, and c and d are each independently an integer of 1 or more and 200 or less, and the sum of a, b, c and d is an integer of 10 or more and 200 or less.
- the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula and the compound of the formula (3b).
- an average molecular weight of the compound of the formula (3a) is preferably 2,000-8,000.
- an average molecular weight of the compound of the formula (3b) is preferably 2,000-30,000.
- An average molecular weight of the compound of the formula (3b) is preferably 8,000-30,000 when a surface-treating layer is formed by a dry coating method, for example, vacuum deposition, and is preferably 2,000-10,000, in particular 3,000-5,000 when a surface-treating layer is formed by using a wet coating method, for example, spray coating.
- an average molecular weight of the fluorine-containing oil may be higher than an average molecular weight of the compound of the formula (1a) and the formula (1b).
- the fluorine-containing oil may be a compound of the general formula Rf'-F wherein Rf' is a C 5-16 perfluoroalkyl group.
- Rf'-F is preferable because the compound has high affinity for the compound of the formula (1a) and the formula (1b) wherein Rf is a C 1-16 perfluoroalkyl group.
- the fluorine-containing oil contributes to increasing of surface slip property of the surface-treating layer.
- silicone oil examples include, for example, a liner or cyclic silicone oil having 2,000 or less siloxane bonds.
- the liner silicone oil may be so-called a straight silicone oil and a modified silicon oil.
- the straight silicone oil examples include dimethylsilicone oil, methylphenylsilicone oil, and methylhydrogensilicone oil.
- the modified silicone oil examples include that which is obtained by modifying a straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, or the like.
- the cyclic silicone oil include, for example, cyclic dimethylsiloxane oil.
- the silicone oil may be contained in the surface-treating agent of the present invention, for example, at 0-300 parts by mass, preferably 50-200 parts by mass with respect to 100 parts by mass of the PFPE containing silane compound of the present invention (as the total mass when two or more compounds are used; hereinafter the same shall apply).
- the silicone oil contributes to increasing of surface slip property of the surface-treating layer.
- Examples of the above-mentioned catalyst include an acid (for example, acetic acid, trifluoroacetic acid, etc.), a base (for example, ammonia, triethylamine, diethylamine, etc.), a transition metal (for example, Ti, Ni, Sn, etc.), and the like.
- an acid for example, acetic acid, trifluoroacetic acid, etc.
- a base for example, ammonia, triethylamine, diethylamine, etc.
- a transition metal for example, Ti, Ni, Sn, etc.
- the catalyst facilitates hydrolysis and dehydration-condensation of the PFPE containing silane compound of the present invention to facilitate a formation of the surface-treating layer.
- Examples of the other components other than the above-mentioned components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.
- the surface-treating agent of the present invention is impregnated into a porous material, for example, a porous ceramic material, a metal fiber for example that obtained by solidifying a steel wool to obtain a pellet.
- a porous material for example, a porous ceramic material, a metal fiber for example that obtained by solidifying a steel wool to obtain a pellet.
- the pellet can be used, for example, in vacuum deposition.
- the article of the present invention comprises a base material and a layer (surface-treating layer) which is formed from the PFPE containing silane compound or the surface-treating agent of the present invention (hereinafter, referred to simply as "surface-treating agent" as a representative thereof) on the surface of the base material.
- This article can be produced, for example, as follows.
- the base material usable in the present invention may be composed of any suitable material such as a glass, a resin (may be a natural or synthetic resin such as a common plastic material, and may be in form of a plate, a film, or others), a metal (may be a simple substance of a metal such as aluminum, copper, or iron, or a complex such as alloy or the like), a ceramic, a semiconductor (silicon, germanium, or the like), a fiber (a fabric, a non-woven fabric, or the like), a fur, a leather, a wood, a pottery, a stone, an architectural member or the like.
- a resin may be a natural or synthetic resin such as a common plastic material, and may be in form of a plate, a film, or others
- a metal may be a simple substance of a metal such as aluminum, copper, or iron, or a complex such as alloy or the like
- a ceramic a semiconductor (silicon, germanium, or the like)
- a fiber a fabric
- a material constituting the surface of the base material may be a material for an optical member, for example, a glass or a transparent plastic.
- any layer (or film) such as a hard coating layer or an antireflection layer may be formed on the surface (outermost layer) of the base material.
- the antireflection layer either a single antireflection layer or a multi antireflection layer may be used.
- Examples of an inorganic material usable in the antireflection layer include SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , CeO 2 , MgO, Y 2 O 3 , SnO 2 , MgF 2 , WO 3 , and the like. These inorganic materials may be used alone or in combination with two or more (for example, as a mixture). When multi antireflection layer is formed, preferably, SiO 2 and/or SiO are used in the outermost layer.
- an article to be produced is an optical glass part for a touch panel, it may have a transparent electrode, for example, a thin layer comprising indium tin oxide (ITO), indium zinc oxide, or the like on a part of the surface of the base material (glass).
- the base material may have an insulating layer, an adhesive layer, a protecting layer, a decorated frame layer (I-CON), an atomizing layer, a hard coating layer, a polarizing film, a phase difference film, a liquid crystal display module, and the like, depending on its specific specification.
- the shape of the base material is not specifically limited.
- the region of the surface of the base material on which the surface-treating layer should be formed may be at least a part of the surface of the base material, and may be appropriately determined depending on use, the specific specification, and the like of the article to be produced.
- the base material may be that of which at least the surface consists of a material originally having a hydroxyl group.
- a material originally having a hydroxyl group examples include a glass, in addition, a metal on which a natural oxidized film or a thermal oxidized film is formed (in particular, a base metal), a ceramic, a semiconductor, and the like.
- the hydroxyl groups when the hydroxyl groups are present but not sufficient, or when the hydroxyl group is originally absent, the hydroxyl group can be introduced on the surface of the base material, or the number of the hydroxyl group can be increased by subjecting the base material to any pretreatment.
- the pretreatment include a plasma treatment (for example, corona discharge) or an ion beam irradiation.
- the plasma treatment may be suitably used to introduce the hydroxyl group into or increase it on the surface of the base material, further, to clarify the surface of the base material (remove foreign materials, and the like).
- the pretreatment include a method wherein a monolayer of a surface adsorbent having a carbon-carbon unsaturated bond group is formed on the surface of the base material by using a LB method (Langmuir-Blodgett method) or a chemical adsorption method beforehand, and then, cleaving the unsaturated bond under an atmosphere of oxygen and nitrogen.
- the base material may be that of which at least the surface consists of a material comprising other reactive group such as a silicon compound having one or more Si-H groups or alkoxysilane.
- the film of the above surface-treating agent of the present invention is formed on the surface of the base material, and the film is post-treated, as necessary, and thereby the surface-treating layer is formed from the surface-treating agent.
- the formation of the film of the surface-treating agent of the present invention can be performed by applying the above surface-treating agent on the surface of the base material such that the surface-treating agent coats the surface.
- the method of coating is not specifically limited. For example, a wet coating method or a dry coating method can be used.
- wet coating method examples include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and a similar method.
- Examples of the dry coating method include deposition (usually, vacuum deposition), sputtering, CVD and a similar method.
- the specific examples of the deposition method include resistance heating, electron beam, high-frequency heating using microwave, etc., ion beam, and a similar method.
- the specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD and a similar method. The deposition method is will be described below in more detail.
- coating can be performed by an atmospheric pressure plasma method.
- the surface-treating agent of the present invention is diluted with a solvent, and then it is applied to the surface of the base material.
- the following solvents are preferably used: an aliphatic perfluorohydrocarbon having 5-12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); an aromatic polyfluorohydrocarbon (for example, bis(trifluoromethyl)benzene); an aliphatic polyfluorohydrocarbon (for example, C 6 F 13 CH 2 CH 3 (for example, ASAHIKLIN (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEORORA (registered trademark) H manufactured by Nippon Zeon
- hydrofluoroether is preferable, perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) and/or perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ) are particularly preferable.
- the surface-treating agent of the present invention may be directly subjected to the dry coating method, or may be diluted with a solvent, and then subjected to the dry coating method.
- the formation of the film is preferably performed so that the surface-treating agent of the present invention is present together with a catalyst for hydrolysis and dehydration-condensation in the coating.
- the catalyst may be added to the diluted solution of the surface-treating agent of the present invention.
- the surface-treating agent of the present invention to which a catalyst has been added is used itself in deposition (usually, vacuum deposition), or pellets may be used in the deposition (usually, the vacuum deposition), wherein the pellets is obtained by impregnating a porous metal such as iron or copper with the surface-treating agent of the present invention to which the catalyst has been added.
- any suitable acid or base can be used.
- the acid catalyst for example, acetic acid, formic acid, trifluoroacetic acid, or the like can be used.
- the base catalyst for example, ammonia, an organic amine, or the like can be used.
- This post-treatment is, but not limited to, a treatment in which water supplying and dry heating are sequentially performed, in more particular, may be performed as follows.
- water is supplied to this film (hereinafter, referred to as precursor coating).
- the method of supplying water may be, for example, a method using dew condensation due to the temperature difference between the precursor coating (and the base material) and ambient atmosphere or spraying of water vapor (steam), but not specifically limited thereto.
- water when water is supplied to the precursor coating, water acts on a hydrolyzable group bonding to Si present in the perfluoro (poly) ether group containing silane compound in the surface-treating agent of the present invention, thereby enabling rapid hydrolysis of the compound.
- the supplying of water may be performed under an atmosphere, for example, at a temperature of 0-250°C, preferably 60°C or more, more preferably 100°C or more and preferably 180°C or less, more preferably 150°C.
- a temperature of 0-250°C preferably 60°C or more, more preferably 100°C or more and preferably 180°C or less, more preferably 150°C.
- the pressure at this time is not specifically limited but simply may be ambient pressure.
- the precursor coating is heated on the surface of the base material under a dry atmosphere over 60°C.
- the method of dry heating may be to place the precursor coating together with the base material in an atmosphere at a temperature over 60°C, preferably over 100°C, and for example, of 250°C or less, preferably of 180°C or less, and at unsaturated water vapor pressure, but not specifically limited thereto.
- the pressure at this time is not specifically limited but simply may be ambient pressure.
- the groups (being hydroxyl groups when all R 1 are hydroxyl groups in the above mentioned compound of any of the formula (1a) or the formula (1b); hereinafter the same shall apply) bonding to Si after hydrolysis are rapidly dehydration-condensed with each other. Furthermore, between the compound and the base material, the group bonding to Si in the compound after hydrolysis and a reactive group present on the surface of the base material are rapidly reacted, and when the reactive group present on the surface of the base material is a hydroxyl group, dehydration-condensation is caused.
- the bond between the PFPE containing silane compounds of the present invention is formed, and the bond between the compound and the base material is formed. It is noted that if present, the fluorine-containing oil and/or the silicone oil is held or acquired by an affinity to the perfluoropolyether group containing silane compound.
- the above supplying of water and dry heating may be sequentially performed by using a superheated water vapor.
- the superheated water vapor is a gas which is obtained by heating a saturated water vapor to a temperature over the boiling point, wherein the gas, under an ambient pressure, has become to have a unsaturated water vapor pressure by heating to a temperature over 100°C, generally of 250°C or less, for example, of 180°C or less, and over the boiling point.
- the temperature difference between the superheated water vapor and the precursor coating decreases, water on the surface of the precursor coating is evaporated under the dry atmosphere of the superheated water vapor, and an amount of water on the surface of the precursor coating gradually decreases.
- the amount of water on the surface of the precursor coating is decreasing, that is, during the precursor coating is under the dry atmosphere, the precursor coating on the surface of the base material contacts with the superheated water vapor, as a result, the precursor coating is heated to the temperature of the superheated water vapor (temperature over 100°C under ambient pressure). Therefore, by using a superheated water vapor, supplying of water and dry heating are enabled to be sequentially carried out simply by exposing the base material on which the precursor coating is formed to a superheated water vapor.
- the post-treatment can be performed. It is noted that though the post-treatment may be performed in order to further increase friction durability, it is not essential in the producing of the article of the present -invention. For example, after applying the surface-treating agent to the surface of the base material, it may be enough to only stand the base material.
- the surface-treating layer derived from the film of the surface-treating agent of the present invention is formed on the surface of the base material to produce the article of the present invention.
- the surface-treating layer thus formed has high surface slip property and high friction durability.
- this surface-treating layer may have water-repellency, oil-repellency, antifouling property (for example, preventing from adhering a fouling such as fingerprints), waterproof property (preventing the ingress of water into an electrical member, and the like), surface slip property (or lubricity, for example, wiping property of a fouling such as fingerprints and excellent tactile feeling in a finger) depending on a composition of the surface-treating agent used, in addition to high friction durability, thus may be suitably used as a functional thin film.
- the present invention further provides an optical material having the hardened material on the outermost layer.
- optical material examples include preferably a variety of optical materials in addition to the optical material for displays, or the like exemplified in below: for example, displays such as a cathode ray tube (CRT; for example, TV, personal computer monitor), a liquid crystal display, a plasma display, an organic EL display, an inorganic thin-film EL dot matrix display, a rear projection display, a vacuum fluorescent display (VFD), a field emission display (FED; Field Emission Display), or a protective plate of such displays, or that in which these displays and protective plates have been subjected to antireflection treatment on their surface.
- displays such as a cathode ray tube (CRT; for example, TV, personal computer monitor), a liquid crystal display, a plasma display, an organic EL display, an inorganic thin-film EL dot matrix display, a rear projection display, a vacuum fluorescent display (VFD), a field emission display (FED; Field Emission Display), or a protective plate of such displays, or that in which these
- the article having the surface-treating layer obtained according to the present invention is not specifically limited to, but may be an optical member.
- the optical member include the followings: lens of glasses, or the like; a front surface protective plate, an antireflection plate, a polarizing plate, or an anti-glare plate on a display such as PDP and LCD; a touch panel sheet of an instrument such as a mobile phone or a personal digital assistance; a disk surface of an optical disk such as a Blu-ray disk, a DVD disk, a CD-R or MO; an optical fiber, and the like.
- the article having the surface-treating layer obtained according to the present invention may be also a medical equipment or a medical material.
- the thickness of the surface-treating layer is not specifically limited.
- the thickness of the surface-treating layer is within the range of 1-50 nm, 1-30 nm, preferably 1-15 nm, in view of optical performance, surface slip property, friction durability and antifouling property.
- the surface-treating agent of the present invention will be described in detail through Examples, although the present invention is not limited to Examples. It is noted that the occurrence order of the four repeating units (CF 2 O), (CF 2 CF 2 O), (CF(CF 3 )CF 2 O), (CF 2 CF 2 CF 2O ) and (CF 2 CF 2 CF 2 CF 2 O) constituting the perfluoropolyether of is not limited in Examples.
- Pentaerythritol triallyl ether bromo adduct (A): BrCH 2 CH 2 CH 2 CH 2 OCH 2 C(CH 2 OCH 2 CH CH 2 ) 3
- a perfluoropolyether modified alcohol compound of the average composition CF 3 O(CF 2 CF 2 O) 20 (CF 2 O) 16 CF 2 CH 2 OH (with proviso that although the compound comprising a small amount of the repeating units (CF 2 CF 2 CF 2 CF 2 O) and/or (CF 2 CF 2 CF 2 O) in the mixture, it was not taken into consideration since it was a very small amount) (8.96 g), 1,3-bis(trifluoromethyl)benzene (51 g), and KOH (0.39 g) were added and stirred at 70°C.
- Perfluoropolyether group containing silane compound (C) CF 3 O(CF 2 CF 2 O) 20 (CF 2 O) 16 CF 2 CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 C(CH 2 OCH 2 CH 2 C H 2 Si(OMe) 3 ) 3
- perfluoropolyether modified alcohol compound (8.5 g) of the average composition: CF 3 CF 2 CF 2 O(CF 2 CF 2 CF 2 O) 20 CF 2 CF 2 CH 2 OH, 1,3-bis(trifluoromethyl)benzene (45 g) and KOH (0.33 g) were added and stirred at 70°C.
- perfluoropolyether group containing silane compound (E) CF 3 CF 2 CF 2 O(CF 2 CF 2 CF 2 O) 20 CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 C(CH 2 OCH 2 CH 2 CH 2 Si(OMe) 3 ) 3
- Perfluoropolyether group containing silane compound (F) CF 3 O(CF 2 CF 2 O) 20 (CF 2 O) 16 CF 2 C[OCH 2 CH 2 CH 2 Si(OMe) 3 ][CH 2 CH 2 CH 2 Si (OMe) 3 ] 2
- Surface-treating agent 1 prepared in the above was vacuum deposited on a chemical strengthening glass (Gorilla glass manufactured by Corning Incorporated; thickness: 0.7 mm). Processing condition of the vacuum deposition was a pressure of 3.0 x 10 -3 Pa. Firstly, silicon dioxide was deposited on the surface of this chemical strengthening glass in a manner of an electron-beam deposition. Subsequently, the surface-treating agent of 2 mg (that is, it contained of 0.4 mg of Compound (C)) was vacuum-deposited per one plate of the chemical strengthening glass (55 mm x 100 mm). Then, the chemical strengthening glass having the deposited layer was stood under a temperature of 20°C and a humidity of 65% for 24 hours.
- a chemical strengthening glass Gorilla glass manufactured by Corning Incorporated; thickness: 0.7 mm. Processing condition of the vacuum deposition was a pressure of 3.0 x 10 -3 Pa. Firstly, silicon dioxide was deposited on the surface of this chemical strengthening glass in a manner of an electron-beam deposition. Subse
- the surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Compound (E) obtained in Synthesis Example 5 was used in place of Compound (C).
- the surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Compound (F) obtained in Synthesis Example 6 was used in place of Compound (C).
- the surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Compound (G) obtained in Synthesis Example 7 was used in place of Compound (C).
- the surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that perfluoropolyether group containing silane compound (H) shown below was used in place of Compound (C).
- Perfluoropolyether group containing silane compound (H) CF 3 O(CF 2 CF 2 O) 20 (CF 2 O) 16 CF 2 C[OC(O)NHCH 2 CH 2 CH 2 Si(OMe) 3 ][CH 2 CH 2 CH 2 Si(OMe) 3 ] 2
- the surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Control compounds 1-3 shown below were used in place of Compound (C).
- g is an integer of 1-6.
- g is an integer of 1-6.
- a static water contact angle of the surface-treating layers formed on the surface of the base material in the above Examples and Comparative Examples respectively was measured.
- the static water contact angle was measured for 1 ⁇ L of water by using a contact angle measuring instrument (manufactured by KYOWA INTERFACE SCIENCE Co., Ltd.).
- the static water contact angle of the surface-treating layer of which the surface had not still contacted with anything after formation thereof was measured (the number of rubbing is zero).
- a steel wool friction durability evaluation was performed. Specifically, the base material on which the surface-treating layer was formed was horizontally arranged, and then, a steel wool (grade No. 0000, 5 mm x 10 mm x 10 mm) was contacted with the exposed surface of the surface-treating layer and a load of 1000 gf was applied thereon. Then, the steel wool was shuttled at a rate of 140 mm/second while applying the load. The static water contact angle (degree) was measured per 2,500 shuttling.
- the present invention is suitably applied for forming a surface-treating layer on a surface of various base materials, in particular, an optical member in which transparency is required.
Abstract
(Rf-PFPE) β -X-(CRa kRb lRc m)α ··· (1a)
(Rc mRb lRa kC)α-X-PFPE-X-(CRa kRb lRc m)α ··· (1b)
wherein the symbols are as defined in the description.
Description
- The present invention relates to a perfluoro(poly)ether group containing silane compound.
- A certain fluorine-containing silane compound is known to be able to provide excellent water-repellency, oil-repellency, antifouling property, or the like when it is used in a surface treatment of a base material. A layer (hereinafter, referred to as a "surface-treating layer") formed from a surface-treating agent comprising a fluorine-containing silane compound is applied to various base materials such as a glass, a plastic, a fiber and a building material as a so-called functional thin film.
- As such fluorine-containing compound, a perfluoropolyether group containing silane compound which has a perfluoropolyether group in its main molecular chain and a hydrolyzable group bonding to a Si atom in its molecular terminal or terminal portion is known (Patent Documents 1 and 2).
-
- Patent Document 1:
JP 2008-534696 A - Patent Document 2: International Publication No.
97/07155 - The surface-treating layer is requested for high durability to provide a base material with a desired function for a long time. The layer formed from the surface-treating agent containing the perfluoropolyether group containing silane compound has been suitably used in an optical member such as glasses, a touch panel or the like which is required to have light permeability or transparency since it can exert the above functions even in form of a thin film. In particular, in these applications, the friction durability is required to be further improved.
- However, a layer formed from a surface-treating agent containing a conventional perfluoropolyether group containing silane compound described above is no longer necessarily enough to meet the increasing demand to improve the friction durability.
- An object of the present invention is to provide a perfluoro(poly)ether group containing silane compound which is able to form a layer having water-repellency, oil-repellency and antifouling property as well as high friction durability.
- As a result of intensively studying, the inventors of the present invention have found that use of a perfluoropolyether group containing silane compound having a plurality of Si atom having a hydrolyzable group improves friction durability, and the inventors reach the present invention.
- According to the first aspect of the present invention, there is provided a perfluoro(poly)ether group containing silane compound of formula (1a) or formula (1b):
(Rf-PFPE)β-X-(CRa kRb lRc m)α ··· (1a)
(Rc mRb lRa kC)α-X-PFPE-X-(CRa kRb lRc m)α ··· (1b)
wherein: - Rf is each independently at each occurrence an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms;
- PFPE is each independently at each occurrence a group of the formula:
-(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-
wherein a, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is 1 or more, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula; - X is each independently a single bond or a 2-10 valent organic group;
- α is each independently an integer of 1-9;
- β is an integer of 1-9;
- Ra is each independently at each occurrence -Z-CR1 pR2 qR3 r;
- Z is each independently at each occurrence an oxygen atom or a divalent organic group;
- R1 is each independently at each occurrence Ra';
- Ra' has the same definition as that of Ra;
- in Ra, the number of C atoms which are straightly linked via the Z group is up to five;
- R2 is each independently at each occurrence -Y-SiR5 nR6 3-n;
- Y is each independently at each occurrence an oxygen atom or a divalent organic group;
- R5 is each independently at each occurrence a hydroxyl group or a hydrolyzable group;
- R6 is each independently at each occurrence a hydrogen atom or a lower alkyl group;
- n is an integer of 1-3 independently per unit -Y-SiR5 nR6 3-n;
- R3 is each independently at each occurrence a hydrogen atom or a lower alkyl group;
- p is each independently at each occurrence an integer of 0-3;
- q is each independently at each occurrence an integer of 0-3;
- r is each independently at each occurrence an integer of 0-3;
- Rb is each independently at each occurrence -Y-SiR5 nR6 3-n ;
- Rc is each independently at each occurrence a hydrogen atom or a lower alkyl group;
- k is each independently at each occurrence an integer of 0-3;
- 1 is each independently at each occurrence an integer of 0-3; and
- m is each independently at each occurrence an integer of 0-3;
- with the proviso that in the formula at least one q is 2 or 3, or at least one 1 is 2 or 3.
- According to the second aspect of the present invention, there is provided a surface-treating agent comprising the perfluoro(poly)ether group containing silane compound described above.
- According to the third aspect of the present invention, there is provided a pellet comprising the surface-treating agent described above.
- According to the fourth aspect of the present invention, there is provided an article comprising a base material and a layer which is formed on a surface of the base material from the perfluoro(poly)ether group containing silane compound described above or the surface-treating agent described above.
- According to the present invention, there is provided a novel perfluoro(poly)ether group containing silane compound. Furthermore, there is provided a surface treating agent obtained by using the perfluoro(poly)ether group containing silane compound. By using them, the surface-treating layer having water-repellency, oil-repellency and antifouling property as well as excellent friction durability can be formed.
- Hereinafter, the compound of the present invention will be described.
- A "hydrocarbon group" as used herein represents a group containing a carbon atom and a hydrogen atom which is obtained by removing a hydrogen atom from a hydrocarbon. Examples of the hydrocarbon group include, but are not particularly limited to, a hydrocarbon group having 1-20 carbon atoms which may be substituted with one or more substituents, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and the like. The "aliphatic hydrocarbon group" may be straight, branched or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. It is noted that the hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, or the like at its end or in its molecular chain.
- As used herein, examples of the substituent of the "hydrocarbon group" include, but are not particularly limited to, for example a halogen atom; and a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C3-10 cycloalkyl group, a C3-10 unsaturated cycloalkyl group, a 5-10 membered heterocyclyl group, a 5-10 membered unsaturated heterocyclyl group, a C6-10 aryl group, a 5-10 membered heteroaryl group, and the like, which may be substituted by one or more halogen atoms.
- As used herein, an "organic group" represents a group containing a carbon atom. A "2-10 valent organic group" represents a 2-10 valent group containing a carbon atom. Examples of the 2-10 valent organic group include, but are not particularly limited to, a 2-10 valent group obtained by removing 1-9 hydrogen atoms from a hydrocarbon group. For example, examples of the divalent organic group include, but are not particularly limited to, a divalent group obtained by removing one hydrogen atom from a hydrocarbon group from a hydrocarbon group.
- The present invention provides a perfluoro(poly)ether group (hereinafter, also referred to as "PFPE") containing silane compound of the formula (1a) or the formula (1b) (hereinafter, also referred to as "a PFPE containing silane compound of the present invention").
(Rf-PFPE)β-X-(CRa kRb lRc m)α ··· (1a)
(Rc mRb lRa kC)α-X-PFPE-X-(CRa kRb lRc m)α ··· (1b)
- In the formula, Rf is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms.
- The "alkyl group having 1-16 carbon atoms" in the alkyl having 1-16 carbon atoms which may be substituted by one or more fluorine atoms may be straight or branched, and preferably is a straight or branched alkyl group having 1-6 carbon atoms, in particular 1-3 carbon atoms, more preferably a straight alkyl group having 1-3 carbon atoms.
- Rf is preferably an alkyl having 1-16 carbon atoms substituted by one or more fluorine atoms, more preferably a CF2H-C1-15 fluoroalkylene group, more preferably a perfluoroalkyl group having 1-16 carbon atoms.
- The perfluoroalkyl group having 1-16 carbon atoms may be straight or branched, and preferably is a straight or branched perfluoroalkyl group having 1-6 carbon atoms, in particular 1-3 carbon atoms, more preferably a straight perfluoroalkyl group having 1-3 carbon atoms, specifically -CF3, -CF2CF3 or -CF2CF2CF3.
- In the formula described above, PFPE is -(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-, and corresponds to a perfluoro(poly)ether group. Herein, a, b, c and d are each independently 0 or an integer of 1 or more. The sum of a, b, c and d is 1 or more. Preferably, a, b, c and d are each independently an integer of 0 or more and 200 or less, for example an integer of 1 or more and 200 or less, more preferably each independently an integer of 0 or more and 100 or less, for example an integer of 1-200. The sum of a, b, c and d is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less. The occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula. Among these repeating units, the -(OC4F8)-group may be any of -(OCF2CF2CF2CF2)-, - (OCF(CF3)CF2CF2)-,-(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, - (OC(CF3)2CF2)-,-(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)- and-(OCF2CF(C2F5))-, preferably -(OCF2CF2CF2CF2)-. The - (OC3F6)-group may be any of - (OCF2CF2CF2)-, - (OCF(CF3)CF2)- and-(OCF2CF(CF3))-, preferably -(OCF2CF2CF2)-. The -(OC2F4)-group may be any of -(OCF2CF2)- and -(OCF(CF3))-, preferably -(OCF2CF2)-.
- In one embodiment, PFPE is -(OC3F6)b- wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, preferably -(OCF2CF2CF2)b- wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, or - (OCF(CF3)CF2)b- wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, more preferably - (OCF2CF2CF2)b- wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less.
- In another embodiment, PFPE is -(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d- wherein a and b are each independently an integer of 0 or more and 30 or less, c and d are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula; preferably -(OCF2CF2CF2CF2)a-(OCF2CF2CF2)b-(OCF2CF2)c-(OCF2)d-. In one embodiment, PFPE may be -(OC2F4)c-(OCF2)d- wherein c and d are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and the occurrence order of the respective repeating units in parentheses with the subscript c or d is not limited in the formula.
- In one embodiment, In -(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d- described above, a lower limit of a ratio of c to d (hereinafter, referred to as an "c/d ratio") may be 0.2, preferably 0.3, and an upper limit of the c/d ratio may be 1.5, preferably 1.3, more preferably 1.1, further preferably 0.9. By setting the c/d ratio to less than 1.5, slip property and friction durability of the surface-treating layer formed from the compound are more increased. The lower the c/d ratio, the higher the slip property and the higher the friction durability of the surface-treating layer becomes. Additionally, by setting the c/d ratio to 0.2 or more, stability of the compound can be more increased. The higher the c/d ratio, the higher the stability of the compound becomes.
- In further another embodiment, PFPE is a group of - (OC2F4-R8)n"-. In the formula, R8 is a group selected from OC2F4, OC3F6 and OC4F8, or a combination of 2 or 3 groups independently selected from these groups. Examples of the combination of 2 or 3 groups independently selected from OC2F4, OC3F6 and OC4F8 include, but not limited to, for example, -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-,-OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-,-OC4F8OC2F4-, -OC2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-,-OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-,-OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-,-OC4F8OC2F4OC2F4-, and the like. n" is an integer of 2-100, preferably an integer of 2-50. In the above-mentioned formula, OC2F4, OC3F6 and OC4F8 may be straight or branched, preferably straight. In this embodiment, PFPE is preferably -(OC2F4-OC3F6)n"- or -(OC2F4-OC4F8)f-.
- In the formula, X is each independently a single bond or a 2-10 valent organic group. X is recognized to be a linker which connects between a perfluoropolyether moiety (i.e., an Rf-PFPE moiety or -PFPE- moiety) providing mainly water-repellency, surface slip property and the like and a moiety (i.e., a group in parentheses with the subscript α) providing an ability to bind to a base material in the compound of the formula (1a) and (1b). Therefore, X may be any organic group as long as the compound of the formula (1a) and (1b) can stably exist.
- In the formula, α is an integer of 1-9, and β is an integer of 1-9. α and β may be varied depending on the valence number of the X group. In the formula (1a), the sum of α and β is the valence number of X. For example, when X is a 10 valent organic group, the sum of α and β is 10, for example, α is 9 and β is 1, α is 5 and β is 5, or α is 1 and β is 9. When X is a divalent organic group, α and β are 1. In the formula (1b), α is a value obtained by subtracting 1 from the valence number of X.
- X is preferably a 2-7 valent, more preferably 2-4 valent, more preferably a divalent organic group.
- In one embodiment, X is a 2-4 valent organic group, α is 1-3, and β is 1.
- In another embodiment, X is a divalent organic group, α is 1, and β is 1. In this case, the formulae (1a) and (1b) are represented by the following formulae (1a') and (1b').
Rf-PFPE-X-CRa kRb lRc m ··· (1a')
Rc mRb lRa kC-X-PFPE-X-CRa kRb lRc m ··· (1b')
- Examples of X include, but are not particularly limited to, for example a divalent group of the following formula:
-(R31)p'-(Xa)q'-
wherein: - R31 is each independently a single bond, -(CH2)s'- or an o-, m- or p-phenylene group, preferably -(CH2)s'-,
- s' is an integer of 1-20, preferably an integer of 1-6, more preferably an integer of 1-3, further more preferably 1 or 2,
- Xa is -(Xb)l'-,
- Xb is each independently at each occurrence a group selected from the group consisting of -O-, -S-, an o-, m- or p-phenylene group, -C(O)O-, -Si(R33)2-, -(Si(R33)2O)m'-Si(R33)2-, -CONR34-, -O-CONR34-, -NR34- and - (CH2)n'-,
- R33 is each independently at each occurrence a phenyl group, a C1-6 alkyl group or a C1-6 alkoxy group, preferably a phenyl group or a C1-6 alkyl group, more preferably a methyl group,
- R34 is each independently at each occurrence a hydrogen atom, a phenyl group or a C1-6 alkyl group (preferably a methyl group),
- m' is each independently at each occurrence an integer of 1-100, preferably an integer of 1-20,
- n' is each independently at each occurrence an integer of 1-20, preferably an integer of 1-6, more preferably an integer of 1-3,
- l' is an integer of 1-10, preferably an integer of 1-5, more preferably an integer of 1-3,
- p' is 0 or 1,
- q' is 0 or 1, and
- at least one of p' and q' is 1, and the occurrence order of the respective repeating units in parentheses with the subscript p' or q' is not limited in the formula. Here, R31 and Xa (typically, a hydrogen atom in R31 and Xa) may be substituted with one or more substituents selected from a fluorine atom, a C1-3 alkyl group and a C1-3 fluoroalkyl group.
- Preferably, X is
a C1-20 alkylene group,
-R31-Xc-R31-, or
-Xd-R31-
wherein R31 is as defined above. - More preferably, X is
an C1-20 alkylene group,
- (CH2)s'-Xc-,
-(CH2)s'-Xc-(CH2)t'-
-Xd-, or
-xd-(CH2)t'-
wherein s' and t' are as defined above. - In the formula, Xc is
-O-,
-S-,
-C(O)O-,
-CONR34-,
-O-CONR34-,
-Si(R33)2-,
-(Si(R33)2O)m'-Si(R33)2-,
-O-(CH2)u'-(Si(R33)2O)m'-Si(R33)2-,
-O-(CH2)u'-Si(R33)2-O-Si(R33)2-CH2CH2-Si(R33)2-O-Si(R33)2-,
-O-(CH2)u'-Si(OCH3)2OSi(OCH3)2-,
-CONR34-(CH2)u'-(Si(R33)2O)m'-Si(R33)2-,
-CONR34-(CH2)u'-N(R34)-, or
-CONR34-(o-, m- or p-phenylene)-Si(R33)2-
wherein R33, R34 and m' are as defined above, and
u' is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3. Xc is preferably -O-. - In the formula, Xd is
-S-,
-C(O)O-,
-CONR34-,
-CONR34-(CH2)u'-(Si(R33)2O)m'-Si(R33)2-,
-CONR34-(CH2)u'-N(R34)-, or
-CONR34-(o-, m- or p-phenylene)-Si(R33)2-
wherein each of symbols is as defined above. - More preferably, X is
an C1-20 alkylene group,
-(CH2)s'-Xc-(CH2)t'-, or
-Xd-(CH2)t'-
wherein each of symbols is as defined above. - Further more preferably, X is
an C1-20 alkylene group,
-(CH2)s'-O-(CH2)t'-,
-(CH2)s'-(Si(R33)2O)m'-Si(R33)2-(CH2)t'-,
-(CH2)s'-O-(CH2)u'-(Si(R33)2O)-Si(R33)2-(CH2)t'-, or
-(CH2)s'-O-(CH2)t'-Si(R33)2-(CH2)u'-Si(R33)2-(CvH2v)-
wherein R33, m', s', t' and u' are as defined above, and v is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3. - In the formula, -(CvH2v)- may be straight or branched, for example, may be, for example, -CH2CH2-, -CH2CH2CH2-,-CH(CH3)-, -CH(CH3)CH2-.
- X may be substituted with one or more substituents selected from a fluorine atom, a C1-3 alkyl group and a C1-3 fluoroalkyl group (preferably, a C1-3 perfluoroalkyl group).
-
- wherein R41 is each independently a hydrogen atom, a phenyl group, an alkyl group having 1-6 carbon atoms, or a C1-6 alkoxy group, preferably a methyl group;
- D is a group selected from:
- -CH2O(CH2)2-,
- -CH2O(CH2)3-,
- -CF2O(CH2)3-,
- -(CH2)2-,
- -(CH2)3-,
- -(CH2)4-,
- -CONH-(CH2)3-,
- -CON(CH3)-(CH2)3-,
- -CON(Ph)-(CH2)3-(wherein Ph is a phenyl group), and
- E is -(CH2)n- wherein n is an integer of 2-6, and
- D binds to PFPE of the main backbone, and E binds to a group opposite to PFPE.
- Specific examples of X include, for example:
- -CH2O(CH2)2-,
- -CH2O(CH2)3-,
- -CH2O(CH2)6-,
- -CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,
- -CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,
- -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,
- -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-,
- -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-,
- -CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-,
- -CH2OCF2CHFOCF2-,
- -CH2OCF2CHFOCF2CF2-,
- -CH2OCF2CHFOCF2CF2CF2-,
- -CH2OCH2CF2CF2OCF2-,
- -CH2OCH2CF2CF2OCF2CF2-,
- -CH2OCH2CF2CF2OCF2CF2CF2-,
- -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-,
- -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-,
- -CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-,
- -CH2OCH2CHFCF2OCF2-,
- -CH2OCH2CHFCF2OCF2CF2-,
- -CH2OCH2CHFCF2OCF2CF2CF2-,
- -CH2OCH2CHFCF2OCF(CF3)CF2OCF2-,
- -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-,
- -CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-
- -CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3) 2(CH2)2-,
- -CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-,
- -(CH2)2-,
- -(CH2)3-,
- -(CH2)4-,
- -(CH2)5-,
- -(CH2)6-,
- -CONH-(CH2)3-,
- -CON(CH3)-(CH2)3-,
- -CON(Ph)-(CH2)3- (wherein Ph is phenyl),
- -CONH-(CH2)6-,
- -CON(CH3)-(CH2)6-,
- -CON(Ph)-(CH2)6- (wherein Ph is phenyl),
- -CONH-(CH2)2NH(CH2)3-,
- -CONH-(CH2)6NH(CH2)3-,
- -CH2O-CONH-(CH2)3-,
- -CH2O-CONH-(CH2)6-,
- -S-(CH2)3-,
- -(CH2)2S(CH2)3-,
- -CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,
- -CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-,
- -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,
- -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-,
- -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-,
- -CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-
- -C(O)O-(CH2)3-,
- -C(O)O-(CH2)6-,
- -CH2-O-(CH2)3-Si(CH3)2(CH2)2-Si(CH3)2-(CH2)2-,
- -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-,
- -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-,
- -CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-,
- -OCH2-,
- -O(CH2)3-,
- -OCFHCF2-,
- In another embodiment, X is each independently a 3-10 valent organic group.
-
- wherein R41 is each independently a hydrogen atom, a phenyl group, an alkyl group having 1-6 carbon atoms, or a C1-6 alkoxy group, preferably a methyl group;
- in each X1, some of T are a following group which binds to PFPE of the main backbone of the formula (1a) and (1b) :
- -CH2O(CH2)2-,
- -CH2O(CH2)3-,
- -CF2O(CH2)3-,
- -(CH2)2-,
- -(CH2)3-,
- -(CH2)4-,
- -CONH-(CH2)3-,
- -CON(CH3)-(CH2)3-,
- -CON(Ph)-(CH2)3- (wherein Ph is phenyl), or
- some of the other T are -(CH2)n"- (wherein n" is an integer of 2-6) attached to the group opposite to PFPE which is a molecular backbone (i.e., -CRa kRb lRC m in the formula (1a) and (1b)), and
- the others T are each independently a methyl group, a phenyl group, or a C1-6 alkoxy, if present.
- In the formula, Ra is each independently at each occurrence -Z-CR1 pR2 qR3 r.
- In the formula, Z is each independently at each occurrence, an oxygen atom or a divalent organic group.
- Z is preferably a C1-6 alkylene group, - (CH2)g-O-(CH2)h-(wherein g is an integer of 0-6, for example, an integer of 1-6, h is an integer of 0-6, for example, an integer of 1-6) or -phenylene-(CH2)i- (wherein i is an integer of 0-6), more preferably a C1-3 alkylene group. These groups may be substituted with, for example, one or more substituents selected form a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group.
- In the formula, R1 is each independently at each occurrence Ra'. Ra' is as defined for Ra.
- In Ra, the number of C atoms which are linearly connected via Z is up to five. That is, in Ra, when there is at least one R1, there are two or more C atoms which are linearly connected via Z in Ra. The number of such C atoms which are linearly connected via Z is five at most. It is noted that "the number of such C atoms which are linearly connected via Z in Ra is equal to the repeating number of - Z-C- which are linearly connected in Ra.
-
- In the above formula, * represents a position binding to C of the main backbone, and ... represents that a predetermined group other than ZC binds thereto, that is, when all three bonds of a C atom are ..., it means an end point of the repeat of ZC. The number on the right shoulder of C means the number of occurrences of C which is linearly connected via the Z group from *. In other words, in the chain in which the repeat of ZC is completed at C2, "the number of such C atoms which are linearly connected via the Z group in Ra" is 2. Similarly, in the chain in which the repeat of ZC is completed at C3, C4 and C5, respectively, "the number of such C atoms which are linearly connected via the Z group in Ra" is 3, 4 and 5. It is noted that as seen from the above formula, there are some ZC chains, but they need not have the same length and may be have arbitrary length.
-
- In one embodiment, the number of such C atoms which are linearly connected via the Z group in Ra is 1 or 2, preferably 1.
- In the formula, R2 is -Y-SiR5 nR6 3-n.
- Y is each independently at each occurrence a divalent organic group.
- In a preferable embodiment, Y is a C1-6 alkylene group, -(CH2)g'-O-(CH2)h'- (wherein g' is an integer of 0-6, for example, an integer of 1-6, and h' is an integer of 0-6, for example, an integer of 1-6), or -phenylene-(CH2)i'-(wherein i' is an integer of 0-6). These groups may be substituted with, for example, one or more substituents selected form a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group.
- In one embodiment, Y may be a C1-6 alkylene group, -O-(CH2)h'- or -phenylene-(CH2)i'- When Y is the above group, a light resistance, in particular an ultraviolet resistance, may be increased.
- R5 is each independently at each occurrence a hydroxyl group or a hydrolyzable group.
- The "hydrolyzable group" as used herein represents a group which is able to undergo a hydrolysis reaction. Examples of the hydrolyzable group include -OR, -OCOR, -ON=C(R)2, -N(R)2, -NHR, halogen (wherein R is a substituted or non-substituted alkyl group having 1-4 carbon atoms), preferably -OR (an alkoxy group). Examples of R include a non-substituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group; a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, in particular a non-substituted alkyl group is preferable, a methyl group or an ethyl group is more preferable. The hydroxyl group may be, but is not particularly limited to, a group generated by hydrolysis of a hydrolyzable group.
- Preferably, R5 is -OR wherein R is a substituted or unsubstituted C1-3 alkyl group, more preferably an ethyl group or a methyl group, in particular a methyl group.
- In the formula, R6 is each independently at each occurrence a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1-20 carbon atoms, more preferably an alkyl group having 1-6 carbon atoms, further preferably a methyl group.
- n is an integer of 1-3, preferably 2 or 3, more preferably 3, independently per unit -Y-SiR5 nR6 3-n.
- In the formula, R3 is each independently at each occurrence a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1-20 carbon atoms, more preferably an alkyl group having 1-6 carbon atoms, further preferably a methyl group.
- In the formula, p is each independently at each occurrence an integer of 0-3; q is each independently at each occurrence an integer of 0-3; r is each independently at each occurrence an integer of 0-3. The sum of p, q and r is 3.
- In a preferable embodiment, in Ra' (when Ra' is absent, Ra) at the terminal of Ra, q is preferably 2 or more, for example 2 or 3, more preferably 3.
- In the formula, Rb is each independently at each occurrence -Y-SiR5 nR6 3-n. Y, R5, R6 and n are as defined for R2.
- In the formula, Rc is each independently at each occurrence a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1-20 carbon atoms, more preferably an alkyl group having 1-6 carbon atoms, further preferably a methyl group.
- In the formula, k is each independently at each occurrence an integer of 0-3; 1 is each independently at each occurrence an integer of 0-3; and m is each independently at each occurrence an integer of 0-3. The sum of k, 1 and m is 3.
- In one embodiment, at least one k is 2 or 3, preferably 3.
- In one embodiment, k is 2 or 3, preferably 3.
- In one embodiment, 1 is 2 or 3, preferably 3.
- In the formula (1a) and (1b), at least one q is 2 or 3, or at least one 1 is 2 or 3. That is, there are at least two -Y-SiR5 nR6 3-n groups in the formula.
- In the perfluoro(poly)ether group containing silane compound of the formula (1a) or the formula (1b), an average molecular weight of the Rf-PFPE moiety is not particularly limited to, and is 500∼30,000, preferably 1,500-30,000, more preferably 2,000-10,000.
- The perfluoro(poly)ether group containing silane compound of the formula (1a) or the formula (1b) may have, but are not limited to, an average molecular weight of 5 x 102 - 1 x 105. Among such range, in view of friction durability, the compound has preferably 2,000-32,000, more preferably 2,500-12,000. It is noted that the "average molecular weight" in the present invention means a number average molecular weight, and the "average molecular weight" is defined as a value measured by using 19F-NMR.
- The perfluoro(poly)ether group containing silane compound of the formula (1a) or the formula (1b) can be prepared by a combination of known methods. For example, a compound of the formula (1a') wherein X is a divalent group can be prepared below, although the present invention is not limited thereto.
- A group containing a double bond (preferably allyl), and a halogen (preferably bromo) are introduced into polyol of HO-X-C(YOH)3 (wherein X and Y are each independently a divalent organic group) to obtain a halide having a double bond of Hal-X-C(Y-O-R-CH=CH2)3 (wherein Hal is halogen, for example Br, and R is a divalent organic group, for example an alkylene group). Then, halogen at the terminal is reacted with a perfluoropolyether group containing alcohol of RPFPE-OH (wherein RPFPE is a perfluoropolyether group containing group.) to obtain RPFPE-O-X-C(Y-O-R-CH=CH2)3. Then, -CH=CH2 at the terminal is reacted with HSiCl3 and an alcohol or HSiR5 3 to obtain RPFPE-O-X-C(Y-O-R-CH2-CH2-SiR5 3)3.
- Those skilled in the art can appropriately select a preferable range of a reaction condition for preparing the perfluoro(poly)ether group containing silane compound of the present invention can be selected by those skilled in the art.
- Next, the surface-treating agent of the present invention will be described.
- The surface-treating agent of the present invention comprises at least one the perfluoro(poly)ether group containing silane compound of the formula (1a) or the formula (1b).
- The surface-treating agent of the present invention can provide a base material with water-repellency, oil-repellency, antifouling property, surface slip property and friction durability, and can be suitably used as an antifouling-coating agent or a water-proof coating agent, although the present invention is not particularly limited thereto.
- In one embodiment, the surface-treating agent of the present invention comprises at least one compound of the formula (1a) or the formula (1b) wherein x is a divalent organic group, α and β are 1.
- In one embodiment, the surface-treating agent of the present invention comprises at least one compound of the formula (1a) or the formula (1b) wherein 1 is 3 and n is 3.
- In one embodiment, the surface-treating agent of the present invention comprises the compound of the formula (1a) .
- The above-mentioned surface-treating agent may comprise other components in addition to the compound of the formula (1a) or the formula (1b). Examples of the other components include, but are not particularly limited to, for example, a (non-reactive) fluoropolyether compound which may be also understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter, referred to as "the fluorine-containing oil"), a (non-reactive) silicone compound which may be also understood as a silicone oil (hereinafter referred to as "a silicone oil"), a catalyst, and the like.
- Examples of the above-mentioned fluorine-containing oil include, but are not particularly limited to, for example, a compound of the following general formula (3) (a perfluoro(poly)ether compound).
R21-(OC4F8)a'-(OC3F6)b'-(OC2F4)c'-(OCF2)d'-R22 (3)
- In the formula, R21 represents a C1-16 alkyl group which may be substituted by one or more fluorine atoms (preferably, a C1-16 perfluoroalkyl group), R22 represents a C1-16 alkyl group which may be substituted by one or more fluorine atoms (preferably, a C1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, and more preferably, R21 and R22 is each independently a C1-3 perfluoroalkyl group.
- Subscripts a', b', c' and d' represent the repeating number of each of four repeating units of perfluoropolyether which constitute a main backbone of the polymer, and are each independently an integer of 0 or more and 300 or less, and the sum of a', b', c' and d' is at least 1, preferably 1-300, more preferably 20-300. The occurrence order of the respective repeating units in parentheses with the subscript a', b', c' or d' is not limited in the formulae. Among these repeating units, the -(OC4F8)- group may be any of -(OCF2CF2CF2CF2)-,-(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-,-(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, - (OCF(CF3)CF(CF3))-,-(OCF(C2F5)CF2)- and -(OCF2CF(C2F5))-, preferably-(OCF2CF2CF2CF2). The -(OC3F6)- group may be any of - (OCF2CF2CF2)-, - (OCF(CF3)CF2)- and -(OCF2CF(CF3))-, preferably - (OCF2CF2CF2)-. The -(OC2F4)- group may be any of -(OCF2CF2)- and -(OCF(CF3))-, preferably -(OCF2CF2)-.
- Examples of the perfluoropolyether compound of the above general formula (3) include a compound of any of the following general formulae (3a) and (3b) (may be one compound or a mixture of two or more compounds).
R21-(OCF2CF2CF2)b"-R22 (3a)
R21-(OCF2CF2CF2CF2)a"-(OCF2CF2CF2)b"-(OCF2CF2)c"-(OCF2)d"-R22 (3b)
In these formulae:
R21 and R22 are as defined above; in the formula (3a), b" is an integer of 1 or more and 100 or less; and in the formula (3b), a" and b" are each independently an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less. The occurrence order of the respective repeating units in parentheses with the subscript a", b", c" or d" is not limited in the formulae. - The above-mentioned fluorine-containing oil may have an average molecular weight of 1,000-30,000. By having such average molecular weight, high surface slip property can be obtained.
- The fluorine-containing oil may be contained in the surface-treating agent of the present invention, for example, at 0-500 parts by mass, preferably 0-400 parts by mass, more preferably 25-400 parts by mass with respect to 100 parts by mass of the PFPE containing silane compound of the present invention (as the total mass when two or more compounds are used; hereinafter the same shall apply).
- The compound of the general formula (3a) and the compound of the general formula (3b) may be used alone or in combination. The compound of the general formula (3b) is preferable than the compound of the general formula (3a) since the compound of the general formula (3b) provides higher surface slip property than the compound of the general formula (3a). When they are used in combination, the ratio by mass of the compound of the general formula (3a) to the compound of the general formula (3b) is preferably 1:1 to 1:30, more preferably 1:1 to 1:10. By applying such ratio by mass, a perfluoropolyether group-containing silane-based coating which provides a good balance of surface slip property and friction durability can be obtained.
- In one embodiment, the fluorine-containing oil comprises one or more compounds of the general formula (3b). In such embodiment, the mass ratio of the compound of the formula (1a) or the formula (1b) to the compound of the formula (3b) in the surface-treating agent is preferably 4:1 to 1:4.
- In one preferable embodiment, the surface-treating agent of the present invention comprises the compound of the formula (1a) or the formula (1b) wherein PFPE is - (OCF2CF2CF2)b- (b is an integer of 1-200) and the compound of the formula (3b). By forming a surface-treating layer by using such surface-treating agent with a wet coating method or a vacuum deposition method, preferably vacuum deposition, excellent surface slip property and friction durability can be obtained.
- In one preferable embodiment, the surface-treating agent of the present invention comprises the compound wherein PFPE represents -(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-wherein a and b are each independently an integer of 0 or more and 30 or less, preferably 0 or more and 10 or less, and c and d are each independently an integer of 1 or more and 200 or less, and the sum of a, b, c and d is an integer of 10 or more and 200 or less. The occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula and the compound of the formula (3b). By forming a surface-treating layer by using such surface-treating agent with a wet coating method or a vacuum deposition method, preferably vacuum deposition, more excellent surface slip property and friction durability can be obtained.
- In these embodiments, an average molecular weight of the compound of the formula (3a) is preferably 2,000-8,000.
- In these embodiments, an average molecular weight of the compound of the formula (3b) is preferably 2,000-30,000. An average molecular weight of the compound of the formula (3b) is preferably 8,000-30,000 when a surface-treating layer is formed by a dry coating method, for example, vacuum deposition, and is preferably 2,000-10,000, in particular 3,000-5,000 when a surface-treating layer is formed by using a wet coating method, for example, spray coating.
- In a preferable embodiment, when a surface-treating layer is formed by using vacuum deposition, an average molecular weight of the fluorine-containing oil may be higher than an average molecular weight of the compound of the formula (1a) and the formula (1b). By selecting such average molecular weights of the compound of the formula (1a) and the formula (1b) and the fluorine-containing oil, more excellent surface slip property and friction durability can be obtained.
- From the other point of view, the fluorine-containing oil may be a compound of the general formula Rf'-F wherein Rf' is a C5-16 perfluoroalkyl group. The compound of Rf'-F is preferable because the compound has high affinity for the compound of the formula (1a) and the formula (1b) wherein Rf is a C1-16 perfluoroalkyl group.
- The fluorine-containing oil contributes to increasing of surface slip property of the surface-treating layer.
- Examples of the above-mentioned silicone oil include, for example, a liner or cyclic silicone oil having 2,000 or less siloxane bonds. The liner silicone oil may be so-called a straight silicone oil and a modified silicon oil. Examples of the straight silicone oil include dimethylsilicone oil, methylphenylsilicone oil, and methylhydrogensilicone oil. Examples of the modified silicone oil include that which is obtained by modifying a straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, or the like. Examples of the cyclic silicone oil include, for example, cyclic dimethylsiloxane oil.
- The silicone oil may be contained in the surface-treating agent of the present invention, for example, at 0-300 parts by mass, preferably 50-200 parts by mass with respect to 100 parts by mass of the PFPE containing silane compound of the present invention (as the total mass when two or more compounds are used; hereinafter the same shall apply).
- The silicone oil contributes to increasing of surface slip property of the surface-treating layer.
- Examples of the above-mentioned catalyst include an acid (for example, acetic acid, trifluoroacetic acid, etc.), a base (for example, ammonia, triethylamine, diethylamine, etc.), a transition metal (for example, Ti, Ni, Sn, etc.), and the like.
- The catalyst facilitates hydrolysis and dehydration-condensation of the PFPE containing silane compound of the present invention to facilitate a formation of the surface-treating layer.
- Examples of the other components other than the above-mentioned components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.
- The surface-treating agent of the present invention is impregnated into a porous material, for example, a porous ceramic material, a metal fiber for example that obtained by solidifying a steel wool to obtain a pellet. The pellet can be used, for example, in vacuum deposition.
- Next, the article of the present invention will be described.
- The article of the present invention comprises a base material and a layer (surface-treating layer) which is formed from the PFPE containing silane compound or the surface-treating agent of the present invention (hereinafter, referred to simply as "surface-treating agent" as a representative thereof) on the surface of the base material. This article can be produced, for example, as follows.
- Firstly, the base material is provided. The base material usable in the present invention may be composed of any suitable material such as a glass, a resin (may be a natural or synthetic resin such as a common plastic material, and may be in form of a plate, a film, or others), a metal (may be a simple substance of a metal such as aluminum, copper, or iron, or a complex such as alloy or the like), a ceramic, a semiconductor (silicon, germanium, or the like), a fiber (a fabric, a non-woven fabric, or the like), a fur, a leather, a wood, a pottery, a stone, an architectural member or the like.
- For example, when an article to be produced is an optical member, a material constituting the surface of the base material may be a material for an optical member, for example, a glass or a transparent plastic. For example, when an article to be produced is an optical member, any layer (or film) such as a hard coating layer or an antireflection layer may be formed on the surface (outermost layer) of the base material. As the antireflection layer, either a single antireflection layer or a multi antireflection layer may be used. Examples of an inorganic material usable in the antireflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, and the like. These inorganic materials may be used alone or in combination with two or more (for example, as a mixture). When multi antireflection layer is formed, preferably, SiO2 and/or SiO are used in the outermost layer. When an article to be produced is an optical glass part for a touch panel, it may have a transparent electrode, for example, a thin layer comprising indium tin oxide (ITO), indium zinc oxide, or the like on a part of the surface of the base material (glass). Furthermore, the base material may have an insulating layer, an adhesive layer, a protecting layer, a decorated frame layer (I-CON), an atomizing layer, a hard coating layer, a polarizing film, a phase difference film, a liquid crystal display module, and the like, depending on its specific specification.
- The shape of the base material is not specifically limited. The region of the surface of the base material on which the surface-treating layer should be formed may be at least a part of the surface of the base material, and may be appropriately determined depending on use, the specific specification, and the like of the article to be produced.
- The base material may be that of which at least the surface consists of a material originally having a hydroxyl group. Examples of such material include a glass, in addition, a metal on which a natural oxidized film or a thermal oxidized film is formed (in particular, a base metal), a ceramic, a semiconductor, and the like. Alternatively, as in a resin, when the hydroxyl groups are present but not sufficient, or when the hydroxyl group is originally absent, the hydroxyl group can be introduced on the surface of the base material, or the number of the hydroxyl group can be increased by subjecting the base material to any pretreatment. Examples of the pretreatment include a plasma treatment (for example, corona discharge) or an ion beam irradiation. The plasma treatment may be suitably used to introduce the hydroxyl group into or increase it on the surface of the base material, further, to clarify the surface of the base material (remove foreign materials, and the like). Alternatively, other examples of the pretreatment include a method wherein a monolayer of a surface adsorbent having a carbon-carbon unsaturated bond group is formed on the surface of the base material by using a LB method (Langmuir-Blodgett method) or a chemical adsorption method beforehand, and then, cleaving the unsaturated bond under an atmosphere of oxygen and nitrogen.
- Alternatively, the base material may be that of which at least the surface consists of a material comprising other reactive group such as a silicon compound having one or more Si-H groups or alkoxysilane.
- Next, the film of the above surface-treating agent of the present invention is formed on the surface of the base material, and the film is post-treated, as necessary, and thereby the surface-treating layer is formed from the surface-treating agent.
- The formation of the film of the surface-treating agent of the present invention can be performed by applying the above surface-treating agent on the surface of the base material such that the surface-treating agent coats the surface. The method of coating is not specifically limited. For example, a wet coating method or a dry coating method can be used.
- Examples of the wet coating method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and a similar method.
- Examples of the dry coating method include deposition (usually, vacuum deposition), sputtering, CVD and a similar method. The specific examples of the deposition method (usually, vacuum deposition) include resistance heating, electron beam, high-frequency heating using microwave, etc., ion beam, and a similar method. The specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD and a similar method. The deposition method is will be described below in more detail.
- Additionally, coating can be performed by an atmospheric pressure plasma method.
- When the wet coating method is used, the surface-treating agent of the present invention is diluted with a solvent, and then it is applied to the surface of the base material. In view of stability of the surface-treating agent of the present invention and volatile property of the solvent, the following solvents are preferably used: an aliphatic perfluorohydrocarbon having 5-12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); an aromatic polyfluorohydrocarbon (for example, bis(trifluoromethyl)benzene); an aliphatic polyfluorohydrocarbon (for example, C6F13CH2CH3 (for example, ASAHIKLIN (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEORORA (registered trademark) H manufactured by Nippon Zeon Co., Ltd.); a hydrofluoroether (HFE) (for example, an alkyl perfluoroalkyl ether such as perfluoropropyl methyl ether (C3F7OCH3) (for example, Novec (trademark) 7000 manufactured by Sumitomo 3M Ltd.), perfluorobutyl methyl ether (C4F3OCH3) (for example, Novec (trademark) 7100 manufactured by Sumitomo 3M Ltd.), perfluorobutyl ethyl ether (C4F9OC2H5) (for example, Novec (trademark) 7200 manufactured by Sumitomo 3M Ltd.), and perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (for example, Novec (trademark) 7300 manufactured by Sumitomo 3M Ltd.) (the perfluoroalkyl group and the alkyl group may be liner or branched)), or CF3CH2OCF2CHF2 (for example, ASAHIKLIN (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.) and the like. These solvents may be used alone or as a mixture of 2 or more compound. Among them, the hydrofluoroether is preferable, perfluorobutyl methyl ether (C4F9OCH3) and/or perfluorobutyl ethyl ether (C4F9OC2H5) are particularly preferable.
- When the dry coating method is used, the surface-treating agent of the present invention may be directly subjected to the dry coating method, or may be diluted with a solvent, and then subjected to the dry coating method.
- The formation of the film is preferably performed so that the surface-treating agent of the present invention is present together with a catalyst for hydrolysis and dehydration-condensation in the coating. Simply, when the wet coating method is used, after the surface-treating agent of the present invention is diluted with a solvent, and just prior to applying it to the surface of the base material, the catalyst may be added to the diluted solution of the surface-treating agent of the present invention. When the dry coating method is used, the surface-treating agent of the present invention to which a catalyst has been added is used itself in deposition (usually, vacuum deposition), or pellets may be used in the deposition (usually, the vacuum deposition), wherein the pellets is obtained by impregnating a porous metal such as iron or copper with the surface-treating agent of the present invention to which the catalyst has been added.
- As the catalyst, any suitable acid or base can be used. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid, or the like can be used. As the base catalyst, for example, ammonia, an organic amine, or the like can be used.
- Next, the film is post-treated as necessary. This post-treatment is, but not limited to, a treatment in which water supplying and dry heating are sequentially performed, in more particular, may be performed as follows.
- After the film of the surface-treating agent of the present invention is formed on the surface of the base material as mentioned above, water is supplied to this film (hereinafter, referred to as precursor coating). The method of supplying water may be, for example, a method using dew condensation due to the temperature difference between the precursor coating (and the base material) and ambient atmosphere or spraying of water vapor (steam), but not specifically limited thereto.
- It is considered that, when water is supplied to the precursor coating, water acts on a hydrolyzable group bonding to Si present in the perfluoro (poly) ether group containing silane compound in the surface-treating agent of the present invention, thereby enabling rapid hydrolysis of the compound.
- The supplying of water may be performed under an atmosphere, for example, at a temperature of 0-250°C, preferably 60°C or more, more preferably 100°C or more and preferably 180°C or less, more preferably 150°C. By supplying water at such temperature range, hydrolysis can proceed. The pressure at this time is not specifically limited but simply may be ambient pressure.
- Then, the precursor coating is heated on the surface of the base material under a dry atmosphere over 60°C. The method of dry heating may be to place the precursor coating together with the base material in an atmosphere at a temperature over 60°C, preferably over 100°C, and for example, of 250°C or less, preferably of 180°C or less, and at unsaturated water vapor pressure, but not specifically limited thereto. The pressure at this time is not specifically limited but simply may be ambient pressure.
- Under such atmosphere, between the PFPE containing silane compound of the present inventions, the groups (being hydroxyl groups when all R1 are hydroxyl groups in the above mentioned compound of any of the formula (1a) or the formula (1b); hereinafter the same shall apply) bonding to Si after hydrolysis are rapidly dehydration-condensed with each other. Furthermore, between the compound and the base material, the group bonding to Si in the compound after hydrolysis and a reactive group present on the surface of the base material are rapidly reacted, and when the reactive group present on the surface of the base material is a hydroxyl group, dehydration-condensation is caused. As the result, the bond between the PFPE containing silane compounds of the present invention is formed, and the bond between the compound and the base material is formed. It is noted that if present, the fluorine-containing oil and/or the silicone oil is held or acquired by an affinity to the perfluoropolyether group containing silane compound.
- The above supplying of water and dry heating may be sequentially performed by using a superheated water vapor.
- The superheated water vapor is a gas which is obtained by heating a saturated water vapor to a temperature over the boiling point, wherein the gas, under an ambient pressure, has become to have a unsaturated water vapor pressure by heating to a temperature over 100°C, generally of 250°C or less, for example, of 180°C or less, and over the boiling point. When the base material on which the precursor coating is formed is exposed to a superheated water vapor, firstly, due to the temperature difference between the superheated water vapor and the precursor coating of a relatively low temperature, dew condensation is generated on the surface of the precursor coating, thereby supplying water to the precursor coating. Presently, as the temperature difference between the superheated water vapor and the precursor coating decreases, water on the surface of the precursor coating is evaporated under the dry atmosphere of the superheated water vapor, and an amount of water on the surface of the precursor coating gradually decreases. During the amount of water on the surface of the precursor coating is decreasing, that is, during the precursor coating is under the dry atmosphere, the precursor coating on the surface of the base material contacts with the superheated water vapor, as a result, the precursor coating is heated to the temperature of the superheated water vapor (temperature over 100°C under ambient pressure). Therefore, by using a superheated water vapor, supplying of water and dry heating are enabled to be sequentially carried out simply by exposing the base material on which the precursor coating is formed to a superheated water vapor.
- As mentioned above, the post-treatment can be performed. It is noted that though the post-treatment may be performed in order to further increase friction durability, it is not essential in the producing of the article of the present -invention. For example, after applying the surface-treating agent to the surface of the base material, it may be enough to only stand the base material.
- As described above, the surface-treating layer derived from the film of the surface-treating agent of the present invention is formed on the surface of the base material to produce the article of the present invention. The surface-treating layer thus formed has high surface slip property and high friction durability. Furthermore, this surface-treating layer may have water-repellency, oil-repellency, antifouling property (for example, preventing from adhering a fouling such as fingerprints), waterproof property (preventing the ingress of water into an electrical member, and the like), surface slip property (or lubricity, for example, wiping property of a fouling such as fingerprints and excellent tactile feeling in a finger) depending on a composition of the surface-treating agent used, in addition to high friction durability, thus may be suitably used as a functional thin film.
- Therefore, the present invention further provides an optical material having the hardened material on the outermost layer.
- Examples of the optical material include preferably a variety of optical materials in addition to the optical material for displays, or the like exemplified in below: for example, displays such as a cathode ray tube (CRT; for example, TV, personal computer monitor), a liquid crystal display, a plasma display, an organic EL display, an inorganic thin-film EL dot matrix display, a rear projection display, a vacuum fluorescent display (VFD), a field emission display (FED; Field Emission Display), or a protective plate of such displays, or that in which these displays and protective plates have been subjected to antireflection treatment on their surface.
- The article having the surface-treating layer obtained according to the present invention is not specifically limited to, but may be an optical member. Examples of the optical member include the followings: lens of glasses, or the like; a front surface protective plate, an antireflection plate, a polarizing plate, or an anti-glare plate on a display such as PDP and LCD; a touch panel sheet of an instrument such as a mobile phone or a personal digital assistance; a disk surface of an optical disk such as a Blu-ray disk, a DVD disk, a CD-R or MO; an optical fiber, and the like.
- The article having the surface-treating layer obtained according to the present invention may be also a medical equipment or a medical material.
- The thickness of the surface-treating layer is not specifically limited. For the optical member, the thickness of the surface-treating layer is within the range of 1-50 nm, 1-30 nm, preferably 1-15 nm, in view of optical performance, surface slip property, friction durability and antifouling property.
- Hereinbefore, the article produced by using the surface-treating agent of the present invention is described in detail. It is noted that an application, a method for using or a method for producing the article are not limited to the above exemplification.
- The surface-treating agent of the present invention will be described in detail through Examples, although the present invention is not limited to Examples. It is noted that the occurrence order of the four repeating units (CF2O), (CF2CF2O), (CF(CF3)CF2O), (CF2CF2CF2O) and (CF2CF2CF2CF2O) constituting the perfluoropolyether of is not limited in Examples.
- To a four necked flask of 100 mL provided with a reflux condenser, a thermometer and a stirrer, NaH (4.62 g), and tetrabutylammonium bromide (0.41 g) were added. Then, 1,3-bis(trifluoromethyl)benzene (23 g), 1,4-dibromobutane (42 g), and pentaerythritol triallyl ether (10 g) were added and stirred at 65°C, and then separated and purified to obtain pentaerythritol triallyl ether bromo adduct (A) (5.23 g).
- Pentaerythritol triallyl ether bromo adduct (A):
BrCH2CH2CH2CH2OCH2C(CH2OCH2CH=CH2)3
- To a four necked flask of 100 mL provided with a reflux condenser, a thermometer and a stirrer, a perfluoropolyether modified alcohol compound of the average composition: CF3O(CF2CF2O)20(CF2O)16CF2CH2OH (with proviso that although the compound comprising a small amount of the repeating units (CF2CF2CF2CF2O) and/or (CF2CF2CF2O) in the mixture, it was not taken into consideration since it was a very small amount) (8.96 g), 1,3-bis(trifluoromethyl)benzene (51 g), and KOH (0.39 g) were added and stirred at 70°C. Then, pentaerythritol triallyl ether bromo adduct (A) (3.60 g) obtained in Synthesizing Example 1, and tetrabutylammonium bromide (0.14 g) were added and stirred at 70°C, and then separated and purified to obtain perfluoropolyether group containing allyloxy compound (B) having an allyl group at the terminal (4.86 g).
- Perfluoropolyether group containing allyloxy compound (B) :
CF3O(CF2CF2O)20(CF2O)16CF2CH2OCH2CH2CH2CH2OCH2C(CH2OCH2CH=C H2)3
- To a four necked flask of 50 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing allyloxy compound (B) (3.33 g) obtained in Synthesizing Example 2, 1,3-bis(trifluoromethyl)benzene (7.24 g), and triacetoxysilane (0.01 g) were added and stirred for 30 minutes. Then, trichlorosilane (1.16 g) and a xylene solution (0.03 ml) containing Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at 2% were added and stirred at 60°C for 3 hours. Then, volatile content was distilled off under a reduced pressure to obtain, and a mixture of methanol (0.13 g) and trimethyl orthoformate (5.25 g) was added, and then, stirred at 50°C and separate and purified to obtain perfluoropolyether group containing silane compound (C) having trimethoxysilyl group at the terminal (3.12 g).
- Perfluoropolyether group containing silane compound (C) :
CF3O(CF2CF2O)20(CF2O)16CF2CH2OCH2CH2CH2CH2OCH2C(CH2OCH2CH2C H2Si(OMe)3)3
- To a four necked flask of 100 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether modified alcohol compound (8.5 g) of the average composition: CF3CF2CF2O(CF2CF2CF2O)20CF2CF2CH2OH, 1,3-bis(trifluoromethyl)benzene (45 g) and KOH (0.33 g) were added and stirred at 70°C. Then, pentaerythritol triallyl ether bromo adduct (A) (3.10 g) obtained in Synthesizing Example 1 and tetrabutylammonium bromide (0.12 g) were added and stirred at 70°C, and then separated and purified to obtain perfluoropolyether group containing allyloxy compound (D) having allyl group at the terminal (4.81 g).
- Perfluoropolyether group containing allyloxy compound (D) :
CF3CF2CF2O(CF2CF2CF2O)20CF2CF2CH2OCH2CH2CH2CH2OCH2C(CH2OCH2 CH=CH2)3
- To a four necked flask of 50 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing allyloxy compound (D) (4.5 g) obtained in Synthesizing Example 4, 1,3-bis(trifluoromethyl)benzene (8.87 g), and triacetoxysilane (0.01 g) were added and stirred for 30 minutes. Then, trichlorosilane (1.42 g) and a xylene solution (0.04 ml) containing Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at 2% were added and stirred at 60°C for 3 hours. Then, volatile content was distilled off under a reduced pressure to obtain, and a mixture of methanol (0.16 g) and trimethyl orthoformate (6.44 g) was added, and then, stirred at 50°C and separate and purified to obtain perfluoropolyether group containing silane compound (E) having trimethoxysilyl group at the terminal (4.36 g).
- perfluoropolyether group containing silane compound (E) :
CF3CF2CF2O(CF2CF2CF2O)20CF2CF2CH2OCH2CH2CH2CH2OCH2C(CH2OCH2 CH2CH2Si(OMe)3)3
- To a four necked flask of 50 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing allyloxy compound of CF3O(CF2CF2O)20(CF2O)16CF2C(OCH2CH=CH2)(CH2CH=CH2)2 (5.0 g) (with proviso that although the compound comprising a small amount of the repeating units (CF2CF2CF2CF2O) and/or (CF2CF2CF2O) in the mixture, it was not taken into consideration since it was a very small amount), 1,3-bis(trifluoromethyl)benzene (9.0 g), and triacetoxysilane (0.01 g) were added and stirred for 30 minutes. Then, trichlorosilane (1.50 g) and a xylene solution (0.05 ml) containing Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at 2% were added and stirred at 60°C for 3 hours. Then, volatile content was distilled off under a reduced pressure to obtain, and a mixture of methanol (0.20 g) and trimethyl orthoformate (7.0 g) was added, and then, stirred at 50°C and separate and purified to obtain perfluoropolyether group containing silane compound (F) having trimethoxysilyl group at the terminal (5.32 g).
- Perfluoropolyether group containing silane compound (F) :
CF3O(CF2CF2O)20(CF2O)16CF2C[OCH2CH2CH2Si(OMe)3][CH2CH2CH2Si (OMe)3]2
- To a four necked flask of 50 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing allyloxy compound of CF3CF2CF2O(CF2CF2CF2O)20CF2CF2C(OCH2CH=CH2)(CH2CH=CH2)2 (4.0 g), 1,3-bis(trifluoromethyl)benzene (7.2 g), and triacetoxysilane (0.01 g) were added and stirred for 30 minutes. Then, trichlorosilane (1.20 g) and a xylene solution (0.04 ml) containing Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at 2% were added and stirred at 60°C for 3 hours. Then, volatile content was distilled off under a reduced pressure to obtain, and a mixture of methanol (0.16 g) and trimethyl orthoformate (5.6 g) was added, and then, stirred at 50°C and separate and purified to obtain perfluoropolyether group containing silane compound (G) having trimethoxysilyl group at the terminal (4.4 g).
- Perfluoropolyether group containing silane compound (G):
CF3CF2CF2O(CF2CF2CF2O)20CF2CF2C[OCH2CH2CH2Si(OMe)3][CH2CH2C H2Si(OMe)3]2
- Compound (C) obtained in Synthesizing Example 3 was dissolved in hydrofluoroether (Novec HFE7200 manufactured by Sumitomo 3M Ltd.)) such that the concentration was 20wt% to prepare Surface-treating agent 1.
- Surface-treating agent 1 prepared in the above was vacuum deposited on a chemical strengthening glass (Gorilla glass manufactured by Corning Incorporated; thickness: 0.7 mm). Processing condition of the vacuum deposition was a pressure of 3.0 x 10-3 Pa. Firstly, silicon dioxide was deposited on the surface of this chemical strengthening glass in a manner of an electron-beam deposition. Subsequently, the surface-treating agent of 2 mg (that is, it contained of 0.4 mg of Compound (C)) was vacuum-deposited per one plate of the chemical strengthening glass (55 mm x 100 mm). Then, the chemical strengthening glass having the deposited layer was stood under a temperature of 20°C and a humidity of 65% for 24 hours.
- The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Compound (E) obtained in Synthesis Example 5 was used in place of Compound (C).
- The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Compound (F) obtained in Synthesis Example 6 was used in place of Compound (C).
- The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Compound (G) obtained in Synthesis Example 7 was used in place of Compound (C).
- The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that perfluoropolyether group containing silane compound (H) shown below was used in place of Compound (C).
- Perfluoropolyether group containing silane compound (H) :
CF3O(CF2CF2O)20(CF2O)16CF2C[OC(O)NHCH2CH2CH2Si(OMe)3][CH2CH 2CH2Si(OMe)3]2
- The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Control compounds 1-3 shown below were used in place of Compound (C).
-
CF3O(CF2CF2O)20(CF2O)16CF2CH2OCH2CH2CH2Si(OCH3)3
-
-
- A static water contact angle of the surface-treating layers formed on the surface of the base material in the above Examples and Comparative Examples respectively was measured. The static water contact angle was measured for 1 µL of water by using a contact angle measuring instrument (manufactured by KYOWA INTERFACE SCIENCE Co., Ltd.).
- Firstly, as an initial evaluation, the static water contact angle of the surface-treating layer of which the surface had not still contacted with anything after formation thereof was measured (the number of rubbing is zero). Then, as an evaluation of the friction durability, a steel wool friction durability evaluation was performed. Specifically, the base material on which the surface-treating layer was formed was horizontally arranged, and then, a steel wool (grade No. 0000, 5 mm x 10 mm x 10 mm) was contacted with the exposed surface of the surface-treating layer and a load of 1000 gf was applied thereon. Then, the steel wool was shuttled at a rate of 140 mm/second while applying the load. The static water contact angle (degree) was measured per 2,500 shuttling. The evaluation was stopped when the measured value of the contact angle became to be less than 100 degree. The results are shown in Table 1 (in the table, the symbol "-" represents no measurement).
Table 1 Number of rubbing (times) Contact Angle (degree) Example 1 Example 2 Example 3 Example 4 Example 5 0 113.1 113.8 113.4 113.0 113.2 2500 112.7 112.5 112.1 111.9 111.7 5000 112.3 111.4 112.0 109.5 108.8 7500 112.0 111.2 110.6 109.2 108.4 10000 112.3 108.2 107.1 107.5 107.4 12500 112.2 106.4 105.9 106.2 104.2 15000 111.1 106.1 104.7 104.0 103.8 17500 110.9 104.9 104.8 103.7 103.5 20000 109.6 104.5 103.9 102.6 102.4 22500 108.3 102.7 102.4 102.2 101.9 Comparative Example 1 Comparative Example 2 Comparative Example 3 0 113.0 112.8 113.6 2500 104.0 110.9 108.2 5000 74.3 110.4 92.5 7500 - 107.2 - 10000 - 105.5 - 12500 - 104.2 - 15000 - 95.0 - 17500 - - - 20000 - - - 22500 - - - - As understood from the above results, it was confirmed that Examples 1-5 using the perfluoropolyether group containing silane compound of the present invention having some Si(OMe)3 branching from a carbon atom of the main chain showed improved friction durability in comparison with Comparative Examples 1-3 using the compounds having no such structure.
- The present invention is suitably applied for forming a surface-treating layer on a surface of various base materials, in particular, an optical member in which transparency is required.
Claims (28)
- A perfluoro(poly)ether group containing silane compound of formula (1a) or formula (1b) :
(Rf-PFPE)β -X-(CRa kRb lRc m)α ··· (1a)
(Rc mRb lRa kC)α-X-PFPE-X-(CRa kRb lRc m)α ··· (1b)
wherein:Rf is each independently at each occurrence an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms;PFPE is each independently at each occurrence a group of the formula:
-(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-
wherein a, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is 1 or more, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula;X is each independently a single bond or a 2-10 valent organic group;α is each independently an integer of 1-9;β is an integer of 1-9;Ra is each independently at each occurrence -Z-CR1 pR2 qR3 r ;Z is each independently at each occurrence an oxygen atom or a divalent organic group;R1 is each independently at each occurrence Ra';Ra' has the same definition as that of Ra ;in Ra, the number of C atoms which are straightly linked via the Z group is up to five;R2 is each independently at each occurrence -Y-SiR5 nR6 3-n ;Y is each independently at each occurrence an oxygen atom or a divalent organic group;R5 is each independently at each occurrence a hydroxyl group or a hydrolyzable group;R6 is each independently at each occurrence a hydrogen atom or a lower alkyl group;n is an integer of 1-3 independently per unit -Y-SiR5 nR6 3-n;R3 is each independently at each occurrence a hydrogen atom or a lower alkyl group;p is each independently at each occurrence an integer of 0-3;q is each independently at each occurrence an integer of 0-3;r is each independently at each occurrence an integer of 0-3;Rb is each independently at each occurrence -Y-SiR5 nR6 3-n ;Rc is each independently at each occurrence a hydrogen atom or a lower alkyl group;k is each independently at each occurrence an integer of 0-3;l is each independently at each occurrence an integer of 0-3; andm is each independently at each occurrence an integer of 0-3;with the proviso that in the formula at least one q is 2 or 3, or at least one 1 is 2 or 3. - The perfluoro(poly)ether group containing silane compound according to claim 1 wherein 1 is 3.
- The perfluoro(poly)ether group containing silane compound according to claim 1 or 2 wherein Rf is a perfluoroalkyl group having 1-16 carbon atoms.
- The perfluoro(poly)ether group containing silane compound according to any one of claims 1-3 wherein PFPE is a group of any of the following formulae (i) to (iv):
-(OCF2CF2CF2)b- (i)
wherein b is an integer of 1-200;
-(OCF(CF3)CF2)b- (ii)
wherein b is an integer of 1-200;
-(OCF2CF2CF2CF2)a-(OCF2CF2CF2)b-(OCF2CF2)c-(OCF2)d- (iii)
wherein a and b are each independently an integer of 0-30, c and d are each independently an integer of 1-200, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula;
or
-(OC2F4-R8)n"- (iv)
wherein R8 is a group selected from OC2F4, OC3F6 and OC4F8, or a combination of 2 or 3 groups independently selected from these groups; andn" is an integer of 2-100. - The perfluoro(poly)ether group containing silane compound according to any one of claims 1-4 wherein X is a divalent organic group, and α and β are 1.
- The perfluoro(poly)ether group containing silane compound according to claim 5 wherein X is each independently
-(R31)p'-(X3)q'-
wherein:R31 is a single bond, -(CH2)s'- (wherein s' is an integer of 1-20) or an o-, m- or p-phenylene group;Xa is -(Xb)l'- (wherein l' is an integer of 1-10);Xb is each independently at each occurrence selected from the group consisting of -O-, -S-, an o-, m- or p-phenylene group, -C(O)O-, -Si(R33)2-, -(Si(R33)2O)m'-Si(R33)2- (wherein m' is an integer of 1-100), -CONR34-,-O-CONR34-, -NR34- and -(CH2)n'- (wherein n' is an integer of 1-20) ;R33 is each independently at each occurrence a phenyl group, a C1-6 alkyl group or a C1-6 alkoxy group;R34 is each independently at each occurrence a hydrogen atom, a phenyl group or a C1-6 alkyl group;p' is 0, 1 or 2;q' is 0 or 1;at least one of p' and q' is 1 or more,the occurrence order of the respective repeating units in parentheses with the subscript p' or q' is not limited in the formula; andR31 and Xa may be substituted with one or more substituents selected from a fluorine atom, a C1-3 alkyl group and a C1-3 fluoroalkyl group. - The perfluoro(poly)ether group containing silane compound according to claim 5 or 6 wherein X is each independently selected from the group consisting of:-CH2O(CH2)2-,-CH2O(CH2)3-,-CH2O(CH2)6-,-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-,-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-,-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-CH2OCF2CHFOCF2-,-CH2OCF2CHFOCF2CF2-,-CH2OCF2CHFOCF2CF2CF2-,-CH2OCH2CF2CF2OCF2-,-CH2OCH2CF2CF2OCF2CF2-,-CH2OCH2CF2CF2OCF2CF2CF2-,-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-,-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-,-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-,-CH2OCH2CHFCF2OCF2-,-CH2OCH2CHFCF2OCF2CF2-,-CH2OCH2CHFCF2OCF2CF2CF2-,-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-,-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-,-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2--CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3) 2(CH2)2-,-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-,- (CH2)2-,- (CH2)3-,- (CH2)4-,- (CH2)5-,- (CH2)6-,-CONH-(CH2)3-,-CON(CH3)-(CH2)3-,-CON(Ph)-(CH2)3- (wherein Ph is a phenyl group),-CONH-(CH2)6-,-CON(CH3)-(CH2)6-,-CON(Ph)-(CH2)6- (wherein Ph is a phenyl group),-CONH-(CH2)2NH(CH2)3-,-CONH-(CH2)6NH(CH2)3-,-CH2O-CONH-(CH2)3-,-CH2O-CONH-(CH2)6-,-S-(CH2)3-,-(CH2)2S(CH2)3-,-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-,-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-,-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-,-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2--C(O)O-(CH2)3-,-C(O)O-(CH2)6-,-CH2-O-(CH2)3-Si(CH3)2 -(CH2)2-Si(CH3)2-(CH2)2-,-CH2-O-(CH2)3-Si(CH3)2 -(CH2)2-Si(CH3)2-CH(CH3)-,-CH2-O-(CH2)3-Si(CH3)2 -(CH2)2-Si(CH3)2-(CH2)3-,-CH2-O-(CH2)3-Si(CH3)2 -(CH2)2-Si(CH3)2-CH(CH3)-CH2-,-OCH2-,-O(CH2)3-,-OCFHCF2-,
- The perfluoro(poly)ether group containing silane compound according to any one of claims 1-4 wherein X is each independently a 3-10 valent organic group.
- The perfluoro(poly)ether group containing silane compound according to claim 8 wherein X is each independently selected from the group consisting of:-CH2O(CH2)2-,-CH2O(CH2)3-,-CF2O(CH2)3-,-(CH2)2-,-(CH2)3-,- (CH2)4-,-CONH-(CH2)3-,-CON(CH3)-(CH2)3-,-CON(Ph)-(CH2)3- (wherein Ph is a phenyl group), andat least one of the other T is -(CH2)n- (wherein n is an integer of 2-6) attached to -CRa kRb lRc m in the formulae (1a) and (1b) and the others are each independently a methyl group, a phenyl group, or a alkoxy having 1-6 carbon atoms,R41 is each independently a hydrogen atom, a phenyl group, an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms, andR42 is each independently a hydrogen atom, a C1-6 alkyl group or a C1-6 alkoxy group.
- The perfluoro(poly)ether group containing silane compound according to any one of claims 1-9 wherein Y is a C1-6 alkylene group, -(CH2)g'-O-(CH2)h'- wherein g' is an integer of 0-6, and h' is an integer of 0-6, or -phenylene-(CH2)i'- wherein i' is an integer of 0-6.
- The perfluoro(poly)ether group containing silane compound according to any one of claims 1-10 wherein an average molecular weight of the Rf-PFPE moiety is 500-30,000.
- The perfluoro(poly)ether group containing silane compound according to any one of claims 1-11 having an average molecular weight of 2,000-32,000.
- A surface-treating agent comprising at least one perfluoro(poly)ether group containing silane compound of the formula (1a) and / or the formula (1b) according to any one of claims 1-12.
- The surface-treating agent according to claim 13 further comprising one or more components selected form a fluorine-containing oil, a silicone oil and a catalyst.
- The surface-treating agent according to claim 14 wherein the fluorine-containing oil is one or more compounds of the formula (3):
R21-(OC4F8)a'-(OC3F6)b'-(OC2F4)c'-(OCF2)d'-R22 (3)
wherein:R21 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms;R22 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; anda', b', c' and d' are the repeating number of each of four repeating units of perfluoro(poly)ether which constitutes a main backbone of the polymer, and are each independently an integer of 0 or more and 300 or less, the sum of a', b', c' and d' is 1 or more, and the occurrence order of the respective repeating units in parentheses with the subscript a', b', c' and d' is not limited in the formula. - The surface-treating agent according to claim 14 or 15 wherein the fluorine-containing oil is one or more compounds of the formula (3a) or (3b):
R21-(OCF2CF2CF2)b"-R22 (3a)
R21-(OCF2CF2CF2CF2)a"-(OCF2CF2CF2)b"-(OCF2CF2)c"-(OCF2)d"-R22 (3b)
wherein:R21 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms;R22 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom;in the formula (3a), b" is an integer of 1 or more and 100 or less;in the formula (3b), a" and b" are each independently an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less; andthe occurrence order of the respective repeating units in parentheses with the subscript a", b", c" or d" is not limited in the formula. - The surface-treating agent according to claim 16 comprising at least one compound of the formula (3b).
- The surface-treating agent according to claim 16 or 17 wherein a mass ratio of the perfluoro(poly)ether group containing silane compound of the formula (1a) or the formula (1b) according to any one of claims 1-12 and the compound of the formula (3b) is 4:1-1:4.
- The surface-treating agent according to any one of claims 16-18 wherein the compound of the formula (3a) has a number average molecular weight of 2,000-8,000.
- The surface-treating agent according to any one of claims 16-19 wherein the compound of the formula (3b) has a number average molecular weight of 2,000-30,000.
- The surface-treating agent according to any one of claims 16-20 wherein the compound of the formula (3b) has a number average molecular weight of 8,000-30,000.
- The surface-treating agent according to any one of claims 13-21 further comprising a solvent.
- The surface-treating agent according to any one of claims 13-22 which is used as an antifouling-coating agent or a water-proof coating agent.
- The surface-treating agent according to any one of claims 13-23 for vacuum deposition.
- A pellet containing the surface-treating agent according to any one of claims 13-24.
- An article comprising a base material and a layer which is formed on a surface of the base material from the compound according to any one of claims 1-12 or the surface-treating agent according to any one of claims 13-24.
- The article according to claim 26 wherein the article is an optical member.
- The article according to claim 26 wherein the article is a display.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP20186455.0A EP3766889A1 (en) | 2015-07-31 | 2016-07-13 | Silane compound containing perfluoro(poly)ether group |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP2015152468 | 2015-07-31 | ||
JP2015181146 | 2015-09-14 | ||
JP2015215019 | 2015-10-30 | ||
PCT/JP2016/070721 WO2017022437A1 (en) | 2015-07-31 | 2016-07-13 | Silane compound containing perfluoro(poly)ether group |
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EP20186455.0A Division EP3766889A1 (en) | 2015-07-31 | 2016-07-13 | Silane compound containing perfluoro(poly)ether group |
EP20186455.0A Division-Into EP3766889A1 (en) | 2015-07-31 | 2016-07-13 | Silane compound containing perfluoro(poly)ether group |
Publications (3)
Publication Number | Publication Date |
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EP3333172A1 true EP3333172A1 (en) | 2018-06-13 |
EP3333172A4 EP3333172A4 (en) | 2019-05-08 |
EP3333172B1 EP3333172B1 (en) | 2020-10-21 |
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EP16832716.1A Active EP3333172B1 (en) | 2015-07-31 | 2016-07-13 | Silane compound containing perfluoro(poly)ether group |
EP20186455.0A Withdrawn EP3766889A1 (en) | 2015-07-31 | 2016-07-13 | Silane compound containing perfluoro(poly)ether group |
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US (2) | US10450413B2 (en) |
EP (2) | EP3333172B1 (en) |
JP (6) | JP6123939B1 (en) |
KR (2) | KR20190072677A (en) |
CN (3) | CN107428786B (en) |
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JP2019183160A (en) | 2019-10-24 |
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CN107428786B (en) | 2019-04-30 |
JP2017082194A (en) | 2017-05-18 |
JP2021001350A (en) | 2021-01-07 |
JP2022103273A (en) | 2022-07-07 |
JP6123939B1 (en) | 2017-05-10 |
CN107428786A (en) | 2017-12-01 |
KR20190072677A (en) | 2019-06-25 |
US20190002635A1 (en) | 2019-01-03 |
CN110054769A (en) | 2019-07-26 |
US20190390009A1 (en) | 2019-12-26 |
JP7425351B2 (en) | 2024-01-31 |
JP6575721B1 (en) | 2019-09-18 |
EP3333172B1 (en) | 2020-10-21 |
US10450413B2 (en) | 2019-10-22 |
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